JP2005220122A - Low molecular recyclable type highpervalent iodine reagent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new highpervalent iodine compound having a high reactivity equivalent to or higher than that of a monomeric reagent, and equipped with both of a recovery efficiency and reusing efficiency equivalent to or higher than those of the conventional polymeric reagent. <P>SOLUTION: This highpervalent iodine compound is expressed by general formula [1]. A concrete example of producing the compound is shown in fig. A. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a hypervalent iodine compound useful and recyclable as a low-toxic oxidant instead of a heavy metal oxidant.

  The hypervalent iodine compound is composed of iodine atoms having a trivalent or pentavalent hypervalent state. Since these compounds have the property of returning to a more stable octet state, they have relatively similar reactivity to heavy metal oxidizing agents such as lead (IV), thallium (III), and mercury (II). It is also less toxic than those. Therefore, it is a compound that has attracted attention as a low-toxic oxidant that replaces these heavy metal oxidants because of its high safety and reactivity.

Examples of trivalent hypervalent iodine compounds include iodosylbenzene (PhIO), phenyliodyne diacetate [PhI (OAc) ₂ : PIDA], phenyliodyne bis (trifluoroacetate) [PhI (OCOCF ₃ ) ₂ : PIFA], [Hydroxy (tosyloxy) iodo] benzene [PhI (OH) (OTs)] and other monomer reagents (see Non-Patent Document 1, Non-Patent Document 2, etc.).

  However, these monomer reagents are highly reactive oxidizing agents. However, when they are used as, for example, tosyloxylating agents, benzene and its derivatives by-produced by the oxidation reaction are soluble in organic solvents, so that the oxidation reaction. It is dissolved in the mixture and requires complicated operations such as use of a new solvent and distillation in order to separate and remove it from the target oxidized compound, which is not preferable from the viewpoint of environmental protection. It was.

Therefore, for example, a polymer-supported hypervalent iodine reagent [poly (diacetoxyiodo) styrene: PDAIS] in which a hypervalent iodine compound derivative such as diacetoxyiodo group (-I (OAc) ₂ group) is introduced into polystyrene was developed. (For example, see Non-Patent Document 3). Since these polymer reagents can be easily separated and removed from the reaction mixture after the reaction, they can be recovered and reused. However, these polymer reagents ensure, for example, (1) low solubility and low reactivity compared to monomer reagents, and (2) the efficiency of introduction of iodine reactive sites into the polymer varies depending on the reagent preparation. (3) The polystyrene chain contains protons at the benzyl position, so the polymer deteriorates little by little when used several times, so complete recovery and reuse are difficult. (4) The iodine reaction site is polystyrene Since it is buried in the chain, it takes time to complete the reaction, and excessive reagents are required.

  Under such circumstances, a novel hypervalent iodine compound having a high reactivity equal to or higher than that of a monomer reagent and having a higher recovery efficiency than existing polymer reagents that does not deteriorate upon reuse. It is in the present situation that development is desired.

V. V. Zhdankin, P. J. Stang, Chemical Reviews, 2002, Vol.102, No.7, p.2523-2584 H. Togo, K. Sakuratani, Synlett, 2002, No. 12, p.1966-1975 Shin Okawara, Kosuke Mizuta, “Industrial Chemistry Magazine” Vol. 64, p.232-235 (1961)

  The present invention has been made in view of the situation as described above, and has a high reactivity equivalent to or higher than that of a monomer reagent, and a novel super atom having both recovery efficiency and reuse efficiency higher than that of a conventional polymer reagent. It is an object to provide a monovalent iodine compound.

The present invention relates to a general formula [1]

{Wherein Z is a carbon atom or a formula [2]

And T represents an arylene group or divalent heterocyclic group which may have a substituent, q represents an integer of 1 to 5, and R ¹ represents: General formula [3]

[Wherein R ² and R ³ are each independently an allyl group, cyclopentadienyl group, hydroxyl group, azide group, cyano group, isocyanate group, thiocyanate group, phthalimide group, haloalkyl group, alkoxy group, substituted Aryl group which may have a group, arylthio group which may have a substituent, heterocyclic group, general formula [4]

(Wherein R ⁴ represents an alkyl group, a haloalkyl group, an aryl group optionally having a substituent, a heterocyclic group, a carboxyalkyl group or a carboxyaryl group), an acyloxy group represented by the general formula [5 ]

(Wherein R ⁵ represents an alkyl group, an aryl group which may have a substituent, a heterocyclic group or a camphor group), a general formula [6]

(In the formula, R ⁶ represents an alkyl group or an aryl group which may have a substituent, and R ⁷ represents an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, an alkylsulfonyl group or an arylsulfonyl group. A group represented by the general formula [7]

(Wherein R ⁸ and R ⁹ are each independently a hydrogen atom, a benzenesulfonyl group, a cyano group, an alkyl group, a haloalkyl group, an alkoxy group, an aryl group that may have a substituent, an aralkyl group, or a cyano group. An alkyl group, an alkyl group which may have an oxygen atom, or an acyloxy group (except when R ⁸ and R ⁹ are both hydrogen atoms)), an alkenyl group represented by the general formula [8]

(In the formula, R ¹⁰ represents an alkyl group, an aryl group which may have a substituent, an aralkyl group, a heterocyclic group, an alkyl group which may have an oxygen atom, an acyl group, an alkoxycarbonyl group, an aralkyloxy group. A carbonyl group, a trialkylsilyloxy group, an alkyldiphenylsilyloxy group, a triphenylsilyloxy group, a benzenesulfonyl group, an allyl group or a cyano group.) Or an alkynyl group represented by the general formula [9]

(Wherein R ¹¹ represents an amino-protected amino acid residue). A group represented by the general formula [10]

Wherein, R ¹² is an optionally substituted aryl group, a group represented by the heterocyclic group or the above-mentioned general formula [8], Y ₁ is a halide, BF 4 _- ^{(tetrafluoroborate)} , PF ₆ ^- (hexafluorophosphate), ClO ₄ ^- (perchlorate), HSO ₄ ^- (hydrogensulfate sulfate) or the general formula [11]

(Wherein R ¹³ represents an alkyl group, a haloalkyl group, an aryl group which may have a substituent, or a heterocyclic group) or a general formula [12]

(Wherein R ¹⁴ represents an alkyl group, a haloalkyl group, an aryl group which may have a substituent or a heterocyclic group) and an anion derived from a sulfonic acid. A group represented by the general formula [13]

[Wherein T ₁ represents an alkylene group, an arylene group, a 1,2-diacyloxyethylene group, or a general formula [14]

(Wherein R ¹⁵ represents an amino protecting group and m represents 1 or 2). A group represented by the general formula [15]

Wherein R ¹⁶ represents a lower alkyl group, a halo lower alkyl group or an aryl group which may have a substituent, and a general formula [16]

(Wherein R ¹⁷ and R ¹⁸ each independently represents a nitro group, a cyano group or a benzenesulfonyl group), an ylide group represented by the general formula [17]

(In the formula, Y ₂ represents a halide, tetrafluoroborate, hexafluorophosphate, perchlorate, hydrogen sulfate or a carboxylic acid represented by the general formula [11] or an anion derived from the sulfonic acid represented by the general formula [12]. N represents an integer of 1 to 5, and Z, T, and q are the same as above.) Or an iodosyl group. } Is an invention of a hypervalent iodine compound.

  The hypervalent iodine compound of the present invention has been reused by the presence of benzylic protons in the polystyrene chain, i.e., the iodine body that is a precursor of the hypervalent iodine compound, which the conventional polymer reagent has. When the reagent is re-oxidized to regenerate the reaction reagent, the hypervalent iodine compound can be efficiently recovered and reused without the problem that the deterioration of the polymer proceeds little by little.

  Furthermore, since the hypervalent iodine compound of the present invention has a tetrahedral structure in which the four reaction sites do not interfere with each other, the reaction sites are buried in, for example, the polymer chain that the conventional polymer reagent had. It has high reactivity equivalent to or higher than that of the monomer reagent without problems such as inefficiency and need of an excess reagent, and difficulty in keeping the reaction site introduction efficiency constant.

  In addition, since the hypervalent iodine compound exhibits high solubility in most organic solvents, it is suitable not only for solid-phase reaction systems that do not use solvents, but also for liquid-phase reaction systems. It can be used efficiently and repeatedly with simple post-treatment without increasing the equivalent of reagents in a wide range of reaction systems, from compound library construction through combinatorial synthesis, which requires high yields and high recoveries, to large scales. .

  In the general formula [1], the arylene group of the arylene group which may have a substituent represented by T usually includes those having 6 to 15 carbon atoms. Specifically, for example, a phenylene group Naphthylene group, anthrylene group and the like, among which, for example, p-phenylene group, 2,6-naphthylene group, 1,4-naphthylene group and the like are preferable.

  Examples of the substituent of the arylene group which may have a substituent represented by T include a halogen atom, an alkyl group, a haloalkyl group, a hydroxyalkyl group, a hydroxyhaloalkyl group, a trialkylsilyl group, and a carboxyl group. .

  Examples of the halogen atom exemplified as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, for example, a fluorine atom and a chlorine atom are preferable.

  The alkyl group exemplified as the substituent may be linear, branched or cyclic, and usually includes those having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specifically, for example, a methyl group , Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group N-hexyl group, isohexyl group, sec-hexyl group, tert-hexyl group, neohexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, etc. Groups and the like are preferred.

  As the haloalkyl group exemplified as the substituent, a part or all of the hydrogen atoms in the alkyl group exemplified as the substituent are halogenated (for example, fluorinated, chlorinated, brominated, iodinated, etc.). Yes, it may be linear, branched or cyclic, and usually has 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. Specific examples thereof include fluoromethyl group, chloromethyl group and bromomethyl group. , Iodomethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, triiodomethyl group, trifluoroethyl group, trichloroethyl group, pentafluoroethyl group, pentachloroethyl group, pentabromoethyl group, pentaiodoethyl Group, chloropropyl group, trifluoropropyl group, trichloropropyl group, 1-trifluoromethyltrif Oroethyl, heptafluoropropyl, heptachloropropyl, heptabromopropyl, heptaiodopropyl, trifluorobutyl, trichlorobutyl, nonafluorobutyl, nonachlorobutyl, nonabromobutyl, nonaiodobutyl, undeca Fluoropentyl group, undecachloropentyl group, undecabromopentyl group, undecaiodopentyl group, tridecafluorohexyl group, tridecachlorohexyl group, tridecabromohexyl group, tridecaiodohexyl group, 2,2, 3,3,4,4,5,5-octafluorocyclopentyl group, 1,2,3,4,5,6-hexafluorocyclohexyl group, 1,4-dichlorocyclohexyl group, 1,2,3,4, 5,6-hexachlorocyclohexyl group, etc., among which, for example, trifluoromethyl group, trichloromethyl group, 1 -A trifluoromethyl trifluoroethyl group etc. are preferable.

  Examples of the hydroxyalkyl group and hydroxyhaloalkyl group mentioned as the substituent include all alkyl groups mentioned as the substituent and those in which one hydrogen atom or halogen atom in the haloalkyl group is substituted with a hydroxyl group. Specific examples of the hydroxyalkyl group include a 1-hydroxy-1-methylethyl group. Preferable specific examples of the hydroxyhaloalkyl group include a 1,1-ditrifluoromethyl-1-hydroxymethyl group.

  Examples of the trialkylsilyl group exemplified as the substituent include those in which three hydrogen atoms of the silyl group are each independently independently substituted with an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specifically, for example, trimethylsilyl group (TMS) group, triethylsilyl (TES) group, tripropylsilyl group, triisopropylsilyl (TIPS) group, tert-butyldimethylsilyl (TBDMS) group, texyldimethylsilyl group, etc. Among them, a trimethylsilyl group is preferable.

  In the general formula [1], the heterocycle of the divalent heterocyclic group represented by T is usually one or more, preferably 1 to 2 heteroatoms such as a nitrogen atom, a sulfur atom and an oxygen atom. 5 or 6-membered ones may be mentioned, which may be monocyclic or polycyclic, specifically, for example, thiophene ring, furan ring, 2H-pyrrole ring, pyrrole ring, imidazole ring, pyrazole ring, thiazole ring, 5-membered monocyclic systems such as thiazole ring, isoxazole ring, and furazane ring, for example, 6-membered monocyclic systems such as pyran ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, such as benzofuran ring, isobenzofuran ring, indolizine ring , Isoindole ring, 3H-indole ring, indole ring, 1H-indazole ring, purine ring, benzothiophene ring, etc. condensed bicyclic system consisting of 5 and 6 members, such as chromene ring, 4 H-quinolidine ring, isoquinoline ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinazoline ring, and the like include two bimembered condensed bicyclic systems such as thiophene ring, furan ring, pyrrole, etc. A ring, imidazole ring, thiazole ring, pyridine ring, benzofuran ring, indole ring, benzothiophene ring, quinoline ring and the like are preferable.

  q is an integer of usually 1 to 5, preferably an integer of 1 to 2, and more preferably 1.

In the general formulas [4] to [8], [11] and [12], the alkyl groups represented by R ^{4 to} R ⁶ , R ^{8 to} R ¹⁰ , R ¹³ and R ¹⁴ are linear, It may be either branched or cyclic, and usually has 1 to 16 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Specifically, for example, in the above general formula [2] The same as those exemplified for the alkyl group having 1 to 6 carbon atoms as the substituent of the arylene group which may have a substituent represented by T, n-heptyl group, isoheptyl group, sec-heptyl group, tert -Heptyl, neoheptyl, n-octyl, isooctyl, sec-octyl, tert-octyl, neooctyl, n-nonyl, isononyl, sec-nonyl, tert-nonyl, neononyl, n -Decyl, isodecyl, sec-decyl, tert-decyl Group, neodecyl group, n-undecyl group, isoundecyl group, sec-undecyl group, tert-undecyl group, neoundecyl group, n-dodecyl group, isododecyl group, sec-dodecyl group, tert-dodecyl group, neododecyl group, n-tridecyl group Group, isotridecyl group, sec-tridecyl group, tert-tridecyl group, neotridecyl group, n-tetradecyl group, isotetradecyl group, sec-tetradecyl group, tert-tetradecyl group, neotetradecyl group, n-pentadecyl group, isopenta Decyl, sec-pentadecyl, tert-pentadecyl, neopentadecyl, n-hexadecyl, isohexadecyl, sec-hexadecyl, tert-hexadecyl, neohexadecyl, cycloheptyl, cyclo Examples include octyl group, cyclononyl group, cyclodecyl group, adamantyl group, etc. Group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, etc. tert- butyl group.

In the general formulas [3], [4], [7], [11] and [12], as the haloalkyl group represented by R ^{2 to} R ⁴ , R ⁸ , R ⁹ , R ¹³ and R ¹⁴ , In the general formula [4], part or all of the hydrogen atoms of the alkyl group represented by R ⁴ are halogenated (for example, fluorinated, chlorinated, brominated, iodinated, etc.). The chain may be any of a chain shape, a branched shape, or a cyclic shape, and examples thereof usually have 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms.

  Specific examples include those in which all hydrogen atoms are halogenated, or those in which usually 1 to 20, preferably 1 to 13, more preferably 1 to 9 hydrogen atoms are halogenated. Those in which all hydrogen atoms are halogenated are preferable. For example, the number of carbon atoms of the haloalkyl group mentioned as the substituent of the arylene group which may have a substituent represented by T in the general formula [2] is 1 To 6 examples, perfluoroheptyl group, perchloroheptyl group, perbromoheptyl group, periodoheptyl group, perfluorooctyl group, perchlorooctyl group, perbromooctyl group, periodooctyl group, periodooctyl group Fluorononyl group, perchlorononyl group, perbromononyl group, periodononyl group, perfluorodecyl group, perchlorodecyl group, Bromodecyl group, and perfluoro yaw dodecyl group and the like, among them, preferably a perfluoroalkyl group having 1 to 6 carbon atoms, especially, such as trifluoromethyl group, trifluoroethyl group and the like are more preferable.

In the general formulas [3] and [7], the alkoxy group represented by R ² , R ³ , R ⁸ and R ⁹ may be linear, branched or cyclic, and usually has 1 carbon atom. -10, preferably 1-6, more preferably 1-4, specifically, for example, methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, neobutoxy group, n-pentyloxy group, isopentyloxy group, sec-pentyloxy group, tert-pentyloxy group, neopentyloxy group, n-hexyloxy group, isohexyloxy group Group, sec-hexyloxy group, tert-hexyloxy group, neohexyloxy group, n-heptyloxy group, isoheptyloxy group, sec-heptyloxy group, tert-heptyloxy group, neoheptylo group Xyl group, n-octyloxy group, isooctyloxy group, sec-octyloxy group, tert-octyloxy group, neooctyloxy group, n-nonyloxy group, isononyloxy group, sec-nonyloxy group, tert-nonyloxy group , Neononyloxy group, n-decyloxy group, isodecyloxy group, sec-decyloxy group, tert-decyloxy group, neodecyloxy group, cyclopropoxy group, cyclobutoxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy Group, cyclooctyloxy group, cyclononyloxy group, cyclodecyloxy group and the like. Among them, for example, methoxy group, ethoxy group and the like are preferable.

  Among the alkoxy groups, the cyclic group may further have a substituent. Examples of the substituent include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and a tert-butyl group. And a lower alkyl group having 1 to 4 carbon atoms such as a group. Preferable specific examples of the cyclic alkoxy group having these substituents include, for example, a menthyloxy group.

In the general formulas [3] to [6], [7], [8], [11], [12] and [15], R ^{2 to} R ⁶ , R ^{8 to} R ¹⁰ , R ¹³ and R ^{14 are used.} As the aryl group of the aryl group which may have a substituent represented by R ¹⁶ , those having usually 6 to 25 carbon atoms, preferably 6 to 15 carbon atoms, can be mentioned. A naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, a spirobifluorenyl group and the like can be mentioned. Among them, for example, a phenyl group, a naphthyl group, a fluorenyl group and the like are preferable, and among them, a phenyl group is more preferable.

  Examples of the substituent of the aryl group which may have the substituent include a halogen atom, an alkyl group, a lower alkoxy group, a halo lower alkyl group, an aryl group, a trialkylsilyl group, a nitro group, and a cyano group. It is done.

  As a halogen atom mentioned as a substituent, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Among these, a fluorine atom is preferable.

The alkyl group mentioned as a substituent may be linear, branched or cyclic, and usually has 1 to 16 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Specifically, for example, the same alkyl group represented by R ⁴ in the above general formula [4] is exemplified. Among them, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n- A butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like are preferable.

The lower alkoxy group exemplified as the substituent may be linear, branched or cyclic, and usually includes those having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. general formula [3] are the same as those of the exemplary 1 to 6 carbon atoms alkoxy group represented by in R ² and R ³ in.

The halo-lower alkyl group mentioned as a substituent may be linear, branched or cyclic, and usually has a part or all of hydrogen atoms of an alkyl group having 1 to 6, preferably 1 to 4 carbon atoms. Examples thereof include halogenated (eg, fluorinated, chlorinated, brominated, iodinated, etc.), specifically, for example, a haloalkyl group represented by R ² and R ³ in the above general formula [3] The thing similar to the illustration of C1-C6 is mentioned.

  As an aryl group mentioned as a substituent, a C6-C12 thing is normally mentioned, Specifically, a phenyl group, a biphenyl group, etc. are mentioned, for example.

  Examples of the trialkylsilyl group exemplified as the substituent include those in which three hydrogen atoms of the silyl group are usually substituted with a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Examples include the same trialkylsilyl groups as the substituents of the arylene group which may have a substituent represented by T in the general formula [2]. preferable.

  Among these substituents, for example, fluorine atom, methyl group, ethyl group, methoxy group, ethoxy group, isopropoxy group, trifluoromethyl group, trichloromethyl group, trifluoroethyl group, phenyl group, biphenyl group and the like are preferable.

  Preferred specific examples of the aryl group having a substituent include, for example, tolyl group, xylyl group, cumenyl group, 1,3,5-tri-tert-butylphenyl group, biphenylyl group, terphenyl group, 4-nitrophenyl group, 2,4-dinitrophenyl group, trimethylsilylphenyl group, fluorophenyl group, chlorophenyl group, bromophenyl group, iodophenyl group, methoxyphenyl group, 9,9-dimethylfluorenyl group, 9,9-diethylfluorenyl group 9,9-di-n-propylfluorenyl group, 9,9-di-n-butylfluorenyl group, 9,9-di-n-pentylfluorenyl group, 9,9-di-n -Hexylfluorenyl group, 9,9-di-n-heptylfluorenyl group, 9,9-di-n-octylfluorenyl group, 9,9-di-n-nonylfluorenyl group, 9 , 9-Di-n-decylfluorenyl group, 9,9-di-n-undecylfluorenyl group, 9,9-di-n-dodecylfluorenyl group Group, 9,9-di-n-tridecylfluorenyl group, 9,9-di-n-tetradecylfluorenyl group, 9,9-di-n-pentadecylfluorenyl group, 9,9 -Di-n-hexadecylfluorenyl group and the like.

In the general formula [3], the arylthio group of the arylthio group which may have a substituent represented by R ² and R ³ usually includes those having 6 to 10 carbon atoms, specifically Examples thereof include a phenylthio group and a naphthylthio group, and among them, a phenylthio group is preferable.

  Examples of the substituent of the arylthio group which may have the substituent include a halogen atom, an alkyl group, a lower alkoxy group, a halo-lower alkyl group, an aryl group, a nitro group, a cyano group, and the like. Specific examples of these include those similar to the examples of the substituent of the aryl group which may have the above-described substituent.

In the general formulas [3] to [5], [8] and [10] to [12], examples of the heterocyclic group represented by R ^{2 to} R ⁵ , R ¹⁰ and R ^{12 to} R ¹⁴ include nitrogen. Examples thereof include 5-membered or 6-membered ones having usually 1 or more, preferably 1 to 5 heteroatoms such as atoms, sulfur atoms and oxygen atoms, and may be monocyclic or polycyclic. Nyl group, thienyl group, furyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, isothiazolyl group, isoxazolyl group, flazanyl group and the like 5-membered monocycle such as tetrahydropyranyl group, 2,6-dioxanyl group, pyridyl group, 6-membered monocycles such as pyrazinyl, pyrimidinyl, pyridazinyl, N- (2-pyridone), such as benzothienyl, isobenzofuranyl, indolizinyl, isoindolyl, indol Condensed bicyclic systems consisting of one 5-membered ring and 6-membered ring such as a group, purinyl group, N- (saccharin) group, such as chromenyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group Condensed bicyclic systems consisting of two 6-membered rings such as cinnolinyl group, pteridinyl group, etc., for example, condensed tricyclic systems consisting of one 5-membered ring and two 6-membered rings such as carbazolyl group, such as thiantenyl group, xanthenyl A condensed tricyclic system composed of three 6-membered rings such as a group, phenoxathinyl group, phenanthridinyl group, acridinyl group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenothiazinyl group, phenoxazinyl group, For example, a quinuclidinyl group, a bridged ring system such as 1,4-diazabicyclo [2.2.2] octyl group (DABCO), etc., among them, for example, a furyl group Pyridyl group, thienyl group, imidazolyl group, benzothienyl group, isoquinolyl group, quinolyl group, phenanthrolinyl group and the like are preferable.

In the general formula [4], the carboxyalkyl group represented by R ⁴ may be linear, branched or cyclic, and is usually an alkyl group having 1 to 9, preferably 1 to 4 carbon atoms ( Specific examples of the alkyl group include the same examples as those having 1 to 8 carbon atoms of the alkyl group represented by R ⁴ in the general formula [4].) One of the hydrogen atoms is substituted with a carboxyl group. Specifically, for example, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group, 5-carboxypentyl group, 6-carboxyhexyl group, 7-carboxyheptyl group, 8 -Carboxyoctyl group, 9-carboxynonyl group, 2-carboxycyclopropyl group, 3-carboxycyclobutyl group, 3-carboxycyclopentyl group, 4-carboxycyclohexyl group, etc. In addition, for example, 2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group and the like are preferable.

Examples of the carboxyaryl group represented by R ⁴ include those in which one of hydrogen atoms in an aryl group having 6 to 10 carbon atoms such as a phenyl group and a naphthyl group is substituted with a carboxyl group. Examples include 2-carboxyphenyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 2-carboxynaphthyl group, 3-carboxynaphthyl group, 4-carboxynaphthyl group, 5-carboxynaphthyl group, etc. A 3-carboxyphenyl group, a 4-carboxyphenyl group, a 4-carboxynaphthyl group, a 5-carboxynaphthyl group, and the like are preferable.

In the general formulas [6] and [8], as the alkoxycarbonyl group represented by R ⁷ and R ¹⁰ , the hydrogen atom of the formyl group is an alkoxy group (specific examples of the alkoxy group include those represented by the general formula [3] And the same as the examples of the alkoxy group represented by R ² and R ³ in the above formula.), Which may be linear, branched or cyclic, and usually has 2 to 2 carbon atoms. 11, preferably 2 to 6, and specifically include, for example, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec -Butoxycarbonyl group, tert-butoxycarbonyl group, neobutoxycarbonyl group, n-pentyloxycarbonyl group, isopentyloxycarbonyl group, sec -Pentyloxycarbonyl group, tert-pentyloxycarbonyl group, neopentyloxycarbonyl group, n-hexyloxycarbonyl group, isohexyloxycarbonyl group, sec-hexyloxycarbonyl group, tert-hexyloxycarbonyl group, neohexyloxycarbonyl Group, n-heptyloxycarbonyl group, isoheptyloxycarbonyl group, sec-heptyloxycarbonyl group, tert-heptyloxycarbonyl group, neoheptyloxycarbonyl group, n-octyloxycarbonyl group, isooctyloxycarbonyl group, sec- Octyloxycarbonyl group, tert-octyloxycarbonyl group, neooctyloxycarbonyl group, n-nonyloxycarbonyl group, isononyloxycarbonyl group, sec-nonyloxycarbonyl group, tert-nonyloxycarbo Group, neononyloxycarbonyl group, n-decyloxycarbonyl group, isodecyloxycarbonyl group, sec-decyloxycarbonyl group, tert-decyloxycarbonyl group, neodecyloxycarbonyl group, cyclopropoxycarbonyl group, cyclobutoxycarbonyl Group, cyclopentyloxycarbonyl group, cyclohexyloxycarbonyl group, cycloheptyloxycarbonyl group, cyclooctyloxycarbonyl group, cyclononyloxycarbonyl group, cyclodecyloxycarbonyl group and the like. Among them, for example, methoxycarbonyl group, ethoxycarbonyl group An isopropoxycarbonyl group, a tert-butoxycarbonyl group, and the like are preferable.

In the general formula [6], the aryloxycarbonyl group represented by R ⁷ is a group in which a hydrogen atom of a formyl group is substituted with an aryloxy group, and usually has 7 to 26 carbon atoms, preferably 7 to 14 carbon atoms. Specifically, for example, phenoxycarbonyl group, naphthoxycarbonyl group, anthryloxycarbonyl group, phenanthryloxycarbonyl group, fluorenyloxycarbonyl group, spirobifluorenyloxycarbonyl group, etc. Among them, a phenoxycarbonyl group, a naphthoxycarbonyl group, a fluorenyloxycarbonyl group and the like are preferable, and among them, a phenoxycarbonyl group is more preferable.

  The aryloxycarbonyl group may further have a substituent, and specific examples of such a substituent include an aryl group having 6 to 12 carbon atoms such as a phenyl group and a biphenyl group. Preferable specific examples of the aryloxycarbonyl group having a substituent include a biphenylyloxycarbonyl group and a terphenyloxycarbonyl group.

In the general formulas [6] and [8], the aralkyloxycarbonyl group represented by R ⁷ and R ¹⁰ is a group in which a hydrogen atom of a formyl group is substituted with an aralkyloxy group, and usually has 7 to 7 carbon atoms. Specifically, for example, benzyloxycarbonyl group, phenethyloxycarbonyl group, α-methylbenzyloxycarbonyl group, 1-methyl-1-phenylethyloxycarbonyl group and the like can be mentioned. An oxycarbonyl group is preferred.

In the general formula [6], as the alkylsulfonyl group represented by R ⁷ , the hydroxyl group of the sulfo group is an alkyl group (specific examples of the alkyl group are represented by R ⁴ in the general formula [4] above). And the same as those exemplified for the alkyl group.), Which may be linear, branched or cyclic, and usually has 1 to 16, preferably 1 to 8, more preferably carbon atoms. Include those having 1 to 4, specifically, for example, methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group, n-pentylsulfonyl group, isopentylsulfonyl group, sec-pentylsulfonyl group, tert-pentylsulfonyl group, neopentylsulfonyl group Group, n-hexylsulfonyl group, isohexylsulfonyl group, sec-hexylsulfonyl group, tert-hexylsulfonyl group, neohexylsulfonyl group, n-heptylsulfonyl group, isoheptylsulfonyl group, sec-heptylsulfonyl group, tert-heptyl Sulfonyl group, neoheptylsulfonyl group, n-octylsulfonyl group, isooctylsulfonyl group, sec-octylsulfonyl group, tert-octylsulfonyl group, neooctylsulfonyl group, n-nonylsulfonyl group, isononylsulfonyl group, sec-nonyl Sulfonyl group, tert-nonylsulfonyl group, neononylsulfonyl group, n-decylsulfonyl group, isodecylsulfonyl group, sec-decylsulfonyl group, tert-decylsulfonyl group, neodecylsulfonyl group, n-undecylsulfonyl group, iso Undecylsulfonyl group, sec -Undecylsulfonyl group, tert-undecylsulfonyl group, neoundecylsulfonyl group, n-dodecylsulfonyl group, isododecylsulfonyl group, sec-dodecylsulfonyl group, tert-dodecylsulfonyl group, neododecylsulfonyl group, n-tri Decylsulfonyl group, isotridecylsulfonyl group, sec-tridecylsulfonyl group, tert-tridecylsulfonyl group, neotridecylsulfonyl group, n-tetradecylsulfonyl group, isotetradecylsulfonyl group, sec-tetradecylsulfonyl group, tert-tetradecylsulfonyl group, neotetradecylsulfonyl group, n-pentadecylsulfonyl group, isopentadecylsulfonyl group, sec-pentadecylsulfonyl group, tert-pentadecylsulfonyl group, neopentadecylsulfonyl group, n-hexadecyl group Sulfonyl group, isohex Sadecylsulfonyl group, sec-hexadecylsulfonyl group, tert-hexadecylsulfonyl group, neohexadecylsulfonyl group, cyclopropylsulfonyl group, cyclobutylsulfonyl group, cyclopentylsulfonyl group, cyclohexylsulfonyl group, cycloheptylsulfonyl group, cyclooctyl Examples thereof include a sulfonyl group, a cyclononylsulfonyl group, a cyclodecylsulfonyl group, and among them, for example, a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, an n-butylsulfonyl group, and the like are preferable.

In the general formula [6], the arylsulfonyl group represented by R ⁷ is one in which the hydroxyl group of the sulfo group is substituted with an aryl group, and usually has 6 to 25 carbon atoms, preferably 6 to 10 carbon atoms. Specifically, for example, a benzenesulfonyl group, a naphthalenesulfonyl group, an anthracenesulfonyl group, a phenanthrenesulfonyl group, a fluorenesulfonyl group, a pyrenesulfonyl group, a spirobifluorenesulfonyl group, and the like, among which a benzenesulfonyl group is preferable. .

  The arylsulfonyl group may further have a substituent, and specific examples of these substituents include C6-C12 aryl groups such as a phenyl group and a biphenyl group. Preferable specific examples of the arylsulfonyl group having a substituent include, for example, a biphenylylsulfonyl group and a terphenylsulfonyl group.

In the general formulas [7] and [8], examples of the aralkyl group represented by R ^{8 to} R ¹⁰ include those having 7 to 26 carbon atoms, preferably 7 to 15 carbon atoms. Benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, phenylpropyl group, phenylbutyl group, phenylpentyl group, naphthylmethyl group, naphthylethyl group, fluorenylmethyl group, phenane Examples include tolylmethyl group, anthrylmethyl group, anthrylethyl group, pyrenylmethyl group, spirobifluorenylmethyl group and the like. Among them, for example, benzyl group, phenethylki, α-methylbenzyl group, naphthylmethyl group, phenanthryl A methyl group, a fluorenylmethyl group and the like are preferable, and among them, a benzyl group, a phenethyl group and the like are more preferable.

  The aralkyl group may further have a substituent. Specific examples of these substituents include aryl groups having 6 to 12 carbon atoms such as a phenyl group and a biphenylyl group. Preferable specific examples of the aralkyl group having a substituent include a biphenylylmethyl group and a terphenylmethyl group.

In the general formula [7], as the cyanoalkyl group represented by R ⁸ and R ⁹ , one hydrogen atom in the alkyl group represented by R ⁴ in the general formula [4] is substituted with a cyano group. Among them, for example, cyanomethyl group, cyanoethyl group and the like are preferable.

In the general formulas [7] and [8], the alkyl group which may have an oxygen atom represented by R ^{8 to} R ¹⁰ is usually 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, and more preferably. Is a chain of an alkyl group of 1 to 4 (specific examples of the alkyl group are the same as those of the alkyl group represented by R ⁴ in the general formula [4] having 1 to 10 carbon atoms). Examples thereof include those containing one or more oxygen atoms, preferably 1 to 5, more preferably 1 to 3, specifically, for example, methoxymethyl group, ethoxymethyl group, methoxyethoxymethyl group Ethoxyethoxymethyl group, methoxyethoxyethoxymethyl group, ethoxyethoxyethoxymethyl group, methoxyethoxyethoxyethoxymethyl group, ethoxyethoxyethoxyethoxymethyl group, etc. However, for example, a methoxymethyl group, an ethoxymethyl group, a methoxyethoxymethyl group and the like are preferable.

In the general formula [7], examples of the acyloxy group represented by R ⁸ and R ⁹ include those usually derived from a carboxylic acid having 2 to 18 carbon atoms, preferably 2 to 11 carbon atoms. Acetoxy, propionyloxy, butyryloxy, isobutyryloxy, valeryloxy, isovaleryloxy, pivaloyloxy, lauroyloxy, pentanoyloxy, hexanoyloxy, cyclohexylcarbonyloxy, octanoyloxy Group, nonanoyloxy group, decanoyloxy group, undecanoyloxy group, lauroyloxy group, tridecanoyloxy group, myristoyloxy group, pentadecanoyloxy group, palmitoyloxy group, heptadecanoyloxy group, stearoyloxy group, etc. Derived from aliphatic carboxylic acids For example, those derived from aromatic carboxylic acids such as benzoyloxy group, toluoyloxy group, naphthoyloxy group, fluorenecarbonyloxy group, phenanthrenecarbonyloxy group, anthracenecarbonyloxy group, pyrenecarbonyloxy group, etc. Of these, for example, an acetyloxy group, a pivaloyloxy group, a benzoyloxy group, a naphthoyloxy group, and the like are preferable.

In the general formula [8], examples of the acyl group represented by R ¹⁰ include those derived from a carboxylic acid having 2 to 18 carbon atoms, preferably 2 to 11 carbon atoms. Propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, pentanoyl group, hexanoyl group, cyclohexylcarbonyl group, octanoyl group, nonanoyl group, decanoyl group, undecanoyl group, lauroyl group, tridecanoyl group, myristoyl Derived from aliphatic carboxylic acids such as benzoyl group, naphthoyl group, fluorene carbonyl group, phenanthrene carbonyl group, anthracene carbonyl group, pyrene carbonyl group, etc., derived from aliphatic carboxylic acid such as benzoyl group, pentadecanoyl group, palmitoyl group, heptadecanoyl group, stearoyl group Examples include those derived from aromatic carboxylic acids. Among them, for example, acetyl group, propionyl group, pivaloyl group, benzoyl group, naphthoyl group and the like are preferable.

In the general formula [8], as the trialkylsilyloxy group represented by R ¹⁰ , the three hydrogen atoms of the silyloxy group are each independently an alkyl group usually having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. (Specific examples of the alkyl group include those substituted with 1 to 6 carbon atoms of the alkyl group represented by R ⁴ in the general formula [4]). Specific examples include trimethylsilyloxy group, triethylsilyloxy group, tripropylsilyloxy group, triisopropylsilyloxy group, tert-butyldimethylsilyloxy group, texyldimethylsilyloxy group, and the like. A butyldimethylsilyloxy group is preferred.

As the alkyldiphenylsilyloxy group represented by R ¹⁰ , two hydrogen atoms in the silyloxy group are substituted with phenyl groups, and one hydrogen atom is usually substituted with an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples include diphenylmethylsilyloxy group, tert-butyldiphenylsilyloxy group, and the like.

In the general formula [9], as the amino acid residue of the amino-protected amino acid residue represented by R ¹¹ , the hydrogen atom of the carboxyl group at the C-terminal of the natural or synthetic amino acid is removed, and the amino terminus is further protected. All of which are mentioned, for example, the general formula [18]

(Wherein, R ¹⁹ represents an α-amino acid side chain, and R ²⁰ represents an amino protecting group).

The α-amino acid side chain represented by R ¹⁹ is a side chain on the α carbon of the α-amino acid. Specifically, for example, glycine (R ¹⁹ is an H-group), alanine (R ¹⁹ is CH ₃ -Group), valine (R ¹⁹ is (CH ₃ ) ₂ CH- group), leucine (R ¹⁹ is (CH ₃ ) ₂ CHCH ₂ -group), isoleucine (R ¹⁹ is CH ₃ CH ₃ CH (CH ₃ )- Group), methionine (R ¹⁹ is CH ₃ SCH ₂ CH ₂ group), phenylalanine (R ¹⁹ is PhCH ₂ -group), tryptophan (R ¹⁹ is 3-indolyl group), serine (R ¹⁹ is HO-CH ₂ -group) ), Threonine (R ¹⁹ is CH ₃ CH (OH) — group), cysteine (R ¹⁹ is HS—CH ₂ — group), tyrosine (HO—C ₆ H ₄ —CH ₂ — group), asparagine (R ¹⁹ is R ¹⁹ H ₂ NCOCH ₂ - group), glutamine ^{(R 19} is H ₂ NCOCH ₂ CH ₂ - group), aspartic acid (HOOCCH ₂ - group), glutamic acid (HOOCCH ₂ CH ₂ - group), lysine ^{(R 19} is H ₂ N (CH _{2) 4} - group) Arginine (R ¹⁹ is _{H 2 NC (= NH) NH} (CH 2) 3 - group), histidine (R ¹⁹ is 5-imidazolylmethyl group) include those derived from α- amino acids, and the like.

Those having an amino group on the α-amino acid side chain (for example, tryptophan, asparagine, glutamine, lysine, arginine, histidine, etc.) are further protected with the amino protecting group represented by R ²⁰ above. .

Examples of the amino protecting group represented by R ²⁰ include all those commonly used as protecting groups for the N-terminal of amino acids. Specifically, for example, “TWgreene and PGMWuts, Protective Groups in Organic Synthesis, second edition, chapter” 7, John Wiley & Sons, NY (1991) ”.

  Preferable specific examples of the amino protecting group include methoxycarbonyl group, ethoxycarbonyl group, tert-butoxycarbonyloxy (BOC) group, benzyloxycarbonyl group, 9-fluorenylmethylcarbonyl group, trichloroethylcarbonyl group, trimethylsilylethoxy group. Examples include carbonyl group, allyloxycarbonyl group, formyl group, trifluoroacetyl group, tosyl group, acetyl group, benzoyl group, phthaloyl group, pentafluorobenzoyl group and the like.

In the general formula [10], examples of the aryl group which may have a substituent represented by R ¹² include those having usually 6 to 25 carbon atoms, preferably 6 to 15 carbon atoms. Specifically, for example, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a fluorenyl group, a spirobifluorenyl group, and the like are preferable, among which a phenyl group, a naphthyl group, a fluorenyl group, and the like are preferable. Groups are more preferred.

Examples of the substituent of the aryl group which may have the substituent include a nitro group, a cyano group, a halogen atom, an alkyl group which may have an oxygen atom, an alkoxy group, an acyloxy group, an alkylcarbamoyl group, An alkylsulfonyl group, an alkylphosphonyl group, an alkylphosphonyloxy group, or a general formula [19]

(Wherein, R ²¹ and R ²² each independently represents an alkyl group), and the like.

  Examples of the halogen atom exemplified as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, for example, a fluorine atom and a chlorine atom are preferable.

The alkyl group which may have an oxygen atom exemplified as a substituent is usually one oxygen atom in the chain of the alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. As mentioned above, those containing preferably 1 to 5, more preferably 1 to 3 are mentioned. Specifically, for example, in R ⁸ and R ¹⁰ in the above general formulas [7] and [8] The thing similar to the illustration of the alkyl group which may have the oxygen atom shown may be mentioned.

The alkoxy group mentioned as a substituent may be linear, branched or cyclic, and usually has 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms. Specifically, for example, the same examples as those exemplified for the alkoxy group represented by R ² , R ³ , R ⁸ and R ⁹ in the general formulas [3] and [7] can be given.

Examples of the acyloxy group exemplified as a substituent include those derived from a carboxylic acid having 2 to 18 carbon atoms, preferably 2 to 11 carbon atoms. Specifically, for example, R ^{8 in the} above general formula [7] and include those similar to the exemplary acyloxy group represented by R ^9.

As the alkylcarbamoyl group mentioned as the substituent, one or two hydrogen atoms of the carbamoyl group are each independently an alkyl group having 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms ( Specific examples of the alkyl group include those substituted with the same examples as those having 1 to 10 carbon atoms of the alkyl group represented by R ⁴ in the general formula [4]. Specifically, for example, N-methylcarbamoyl group, N-ethylcarbamoyl group, Nn-propylcarbamoyl group, N-isopropylcarbamoyl group, Nn-butylcarbamoyl group, N-isobutylcarbamoyl group, N-sec-butylcarbamoyl group, N-tert-butylcarbamoyl group, N-neobutylcarbamoyl group, Nn-pentylcarbamoyl group, N-isopentylcarbamoyl group, N-sec-pentylcarbamoyl N-tert-pentylcarbamoyl group, N-neopentylcarbamoyl group, Nn-hexylcarbamoyl group, N-isohexylcarbamoyl group, N-sec-hexylcarbamoyl group, N-tert-hexylcarbamoyl group, N-tert-hexyl Carbamoyl group, N-neohexylcarbamoyl group, Nn-heptylcarbamoyl group, N-isoheptylcarbamoyl group, N-sec-heptylcarbamoyl group, N-tert-heptylcarbamoyl group, N-neoheptylcarbamoyl group, Nn-octylcarbamoyl Group, N-isooctylcarbamoyl group, N-sec-octylcarbamoyl group, N-tert-octylcarbamoyl group, N-neooctylcarbamoyl group, Nn-nonylcarbamoyl group, N-isononylcarbamoyl group, N-sec-noni Rucarbamoyl group, N-tert-nonylcarbamoyl group, N-neonylylcarbamoyl group, N-decylcarbamoyl group N-isodecylcarbamoyl group, N-sec-decylcarbamoyl group, N-tert-decylcarbamoyl group, N-neodecylcarbamoyl group, N-cyclohexylcarbamoyl group, N-cycloheptylcarbamoyl group, N-cyclooctylcarbamoyl group, N, N-dimethylcarbamoyl group, N, N-diethylcarbamoyl group, N, N-di-n-propylcarbamoyl group, N, N-diisopropylcarbamoyl group, N, N-di-n-butylcarbamoyl group, N, N-di-n-pentylcarbamoyl group, N, N-di-n-hexylcarbamoyl group, N, N-di-n-heptylcarbamoyl group, N, N-di-n-octylcarbamoyl group, N, N- Di-n-nonylcarbamoyl group, N, N-di-n-decylcarbamoyl group, N, N-dicyclopentylcarbamoyl group, N, N-dicyclohexylcarbamoyl group and the like can be mentioned, for example, N-methylcarbamoyl group, N-ethylcarbamoyl , N, N-dimethylcarbamoyl group, N, N-diethylcarbamoyl group and the like.

The alkylsulfonyl group mentioned as a substituent may be linear, branched or cyclic, and usually has 1 to 16, preferably 1 to 8, more preferably 1 to 4 carbon atoms. Specific examples thereof include those similar to the alkylsulfonyl group represented by R ⁷ in the general formula [6].

  The alkylphosphonyl group mentioned as a substituent may be linear, branched or cyclic, and usually has 1 to 16 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 4 carbon atoms. Specifically, for example, methylphosphonyl group, ethylphosphonyl group, n-propylphosphonyl group, isopropylphosphonyl group, n-butylphosphonyl group, isobutylphosphonyl group, sec-butylphosphonyl group, tert-butylphosphonyl group, n -Pentylphosphonyl group, isopentylphosphonyl group, sec-pentylphosphonyl group, tert-pentylphosphonyl group, neopentylphosphonyl group, n-hexylphosphonyl group, isohexylphosphonyl group, sec-hexylphosphonyl group Group, tert-hexylphosphonyl group, neohexylphosphonyl group, n-heptylphosphonyl group, isoheptylphosphonyl group, sec-heptylphosphonyl group, tert-heptylphosphonyl group, neoheptylphosphonyl group, n-octylphosphonyl group, isooctylphosphonyl group, sec-octylphosphonyl group, tert-octylphosphonyl group, neooctylphosphon Nyl group, n-nonylphosphonyl group, isononylphosphonyl group, sec-nonylphosphonyl group, tert-nonylphosphonyl group, neononylphosphonyl group, n-decylphosphonyl group, isodecylphosphonyl group, sec-decylphosphonyl group, tert-decylphosphonyl group , Neodecylphosphonyl group, n-undecylphosphonyl group, isoundecylphosphonyl group, sec-undecylphosphonyl group, tert-undecylphosphonyl group, neoundecylphosphonyl group, n-dodecylphosphonyl group Group, isododecylphosphonyl group, sec-dodecylphosphonyl group, tert-dodecylphosphonyl group, Neododecylphosphonyl group, n-tridecylphosphonyl group, isotridecylphosphonyl group, sec-tridecylphosphonyl group, tert-tridecylphosphonyl group, neotridecylphosphonyl group, n-tetradecylphosphonyl group Group, isotetradecylphosphonyl group, sec-tetradecylphosphonyl group, tert-tetradecylphosphonyl group, neotetradecylphosphonyl group, n-pentadecylphosphonyl group, isopentadecylphosphonyl group, sec-penta Decylphosphonyl group, tert-pentadecylphosphonyl group, neopentadecylphosphonyl group, n-hexadecylphosphonyl group, isohexadecylphosphonyl group, sec-hexadecylphosphonyl group, tert-hexadecyl Phosphonyl group, neohexadecylphosphonyl group, cyclopropylphosphonyl group, cyclobutylphosphonyl group, cyclopentyl Examples include sulfonyl group, cyclohexyl phosphonyl group, cycloheptyl phosphonyl group, cyclooctyl phosphonyl group, cyclononyl phosphonyl group, cyclodecyl phosphonyl group, etc., among them, for example, methyl phosphonyl group, ethyl phosphonyl group, n -Propylphosphonyl group, isopropylphosphonyl group, n-butylphosphonyl group, tert-butylphosphonyl group and the like are preferable.

  The alkylphosphonyloxy group mentioned as a substituent may be linear, branched or cyclic, and usually has 1 to 16, preferably 1 to 8, more preferably 1 to 4 carbon atoms. Specifically, all those in which —O— is further bonded to the above alkylphosphonyl group are exemplified, among which, for example, methylphosphonyloxy group, ethylphosphonyloxy group, n-propylphosphonyloxy group, An isopropylphosphonyloxy group, n-butylphosphonyloxy group, tert-butylphosphonyloxy group and the like are preferable.

In the general formula [19], the alkyl group represented by R ²¹ and R ²² may be linear, branched or cyclic, and usually has 1 to 16 carbon atoms, preferably 1 to 6 carbon atoms. preferably include those having 1 to 4, specifically, for example, those similar illustrative and alkyl group represented by in R ⁴ in the general formula [4].

In the general formula [10], examples of the halide represented by Y ₁ include fluoride, chloride, bromide, iodide and the like. Among these, chloride, bromide, iodide and the like are preferable.

In the general formula [13], the alkylene group represented by T ₁ may be linear, branched or cyclic, and usually has 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. Specifically, for example, a linear alkylene group such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, etc. Ethylidene, propylene, isopropylidene, ethylethylene, 1,2-dimethylethylene, 1,2-diethylethylene, 1,2-di-n-propylethylene, 1,2-di-n- A branched alkylene group such as a butylethylene group, such as 1,2-cyclopentylene group, 1,3-cyclopentylene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1, 4-cyclohexylene group, Examples include cyclic alkylene groups such as 1,2-cycloheptylene group and 1,2-cyclooctylene group. Among them, for example, methylene group, ethylene group, 1,2-dimethylethylene group, 1,2-diethylethylene group, 1,2-cyclopentylene group, 1,2-cyclohexylene group and the like are preferable.

Examples of the arylene group represented by T ₁ usually include those having 6 to 15 carbon atoms. Specific examples include an o-phenylene group, an m-phenylene group, a naphthylene group, and an anthrylene group. A -phenylene group, m-phenylene group and the like are preferable.

As the 1,2-diacyloxyethylene group represented by T ₁ , hydrogen atoms at the 1-position and 2-position of the ethylene group are each independently derived from a carboxylic acid usually having 2 to 18 carbon atoms, preferably 2 to 8 carbon atoms. Specific examples thereof include those substituted with an acyloxy group. Specific examples include 1,2-diacetoxyethylene group, 1,2-dipropionyloxyethylene group, 1,2-dibutyryloxyethylene group, 1,2- Diisobutyryloxyethylene group, 1,2-divaleryloxyethylene group, 1,2-diisovaleryloxyethylene group, 1,2-dipivaloyloxyethylene group, 1,2-dilauroyloxyethylene Aliphatic acyloxy such as 1,2-dipentanoyloxyethylene group, 1,2-dihexanoyloxyethylene group, 1,2-dicyclohexylocarbonyloxyethylene group, 1,2-dioctanoyloxyethylene group Substituted ethylene groups, eg Examples thereof include aromatic acyloxy-substituted ethylene groups such as 1,2-dibenzoyloxyethylene group and 1,2-ditoluoxyoxyethylene group. Among them, for example, 1,2-diacetoxyethylene group, 1,2-diethyl Pivaloyloxyethylene group, 1,2-dibenzoyloxyethylene group, 1,2-ditoluoyloxyethylene group and the like are preferable.

In the general formula [14], examples of the amino protecting group represented by R ¹⁵ include all of those commonly used as a protecting group for the N-terminal of amino acids. Specifically, for example, “TWgreene and PGMWuts, Protective "Groups in Organic Synthesis, second edition, chapter 7, John Wiley & Sons, NY (1991)", etc. Preferable specific examples of the amino protecting group include the same examples as the preferred specific examples of the amino protecting group represented by R ²⁰ in the general formula [18].

In the general formula [15], the lower alkyl group represented by R ¹⁶ may be linear, branched or cyclic, and usually has 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specifically, for example, the same alkyl groups represented by R ⁴ in the general formula [4] as those having 1 to 6 carbon atoms are exemplified, and among them, a methyl group is preferable.

The halo-lower alkyl group represented by R ¹⁶ may be linear, branched or cyclic, and usually a part or all of the hydrogen atoms of the alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Examples thereof include halogenated (eg, fluorinated, chlorinated, brominated, iodinated, etc.), specifically, for example, a haloalkyl group represented by R ² and R ³ in the above general formula [3] Examples having 1 to 6 carbon atoms are the same, and among them, a trifluoromethyl group is preferable.

In the general formula [17], examples of the halide represented by Y ₂ include fluoride, chloride, bromide, iodide and the like. Among them, chloride, bromide, iodide and the like are preferable.

n is usually an integer of 1 to 5, preferably an integer of 1 to 3, and more preferably 1.
In the general formula [1], the iodosyl group represented by R ¹ is a group represented by — (IO) p (wherein p represents an integer of 1 to 10), and p is preferably It represents an integer of 1 to 5, more preferably 1 to 3.

  Preferable specific examples of the carboxylic acid represented by the general formula [11] include, for example, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, Nonanoic acid, decanoic acid, undecanoic acid, lauric acid, myristic acid, pentadecanoic acid, aliphatic carboxylic acid such as palmitic acid, aliphatic cyclocarboxylic acid such as cyclohexyl carboxylic acid, such as fluoroacetic acid, trifluoroacetic acid, chloroacetic acid, Haloalkyl carboxylic acids such as benzoic acid, such as dichloroacetic acid, trichloroacetic acid, bromoacetic acid, iodoacetic acid, perfluoropropionic acid, perchloroheptanoic acid, perfluoroheptanoic acid, perfluorooctanoic acid, perfluorodecanoic acid, perfluorododecanoic acid , Naphthoic acid, anthracene carvone Aromatic carboxylic acids such as toluic acid, for example, fluorobenzoic acid, chlorobenzoic acid, bromobenzoic acid, difluorobenzoic acid, dichlorobenzoic acid, dibromobenzoic acid, trifluorobenzoic acid, trichlorobenzoic acid Acid, tribromobenzoic acid, tetrafluorobenzoic acid, tetrachlorobenzoic acid, tetrabromobenzoic acid, pentafluorobenzoic acid, pentachlorobenzoic acid, halogenated aromatic monocarboxylic acids such as pentabromobenzoic acid, such as trifluoromethylbenzoic acid, trichloro Halogenated alkyl aromatic carboxylic acids such as methylbenzoic acid and bis (trifluoromethyl) benzoic acid, nitroaromatic carboxylic acids such as trinitrobenzoic acid, such as nicotinic acid, isonicotinic acid, furancarboxylic acid, thiophenecar Phosphate, such as heterocyclic carboxylic acids such as 1-pyrrole carboxylic acid.

  Preferable specific examples of the sulfonic acid represented by the general formula [12] include, for example, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid, Alkyl sulfonic acids such as nonane sulfonic acid, decane sulfonic acid, undecane sulfonic acid, dodecane sulfonic acid, tridecane sulfonic acid, tetradecane sulfonic acid, pentadecane sulfonic acid, hexadecane sulfonic acid, such as trifluoromethane sulfonic acid, trichloromethane sulfonic acid, tri Bromomethanesulfonic acid, triiodomethanesulfonic acid, pentafluoroethanesulfonic acid, pentachloroethanesulfonic acid, pentabromoethanesulfonic acid, pentaiodoethanesulfonic acid, heptaful Lopropanesulfonic acid, heptachloropropanesulfonic acid, heptabromopropanesulfonic acid, heptaiodopropanesulfonic acid, nonafluorobutanesulfonic acid, nonachlorobutanesulfonic acid, nonabromobutanesulfonic acid, nonaiodobutanesulfonic acid, perfluoropentanesulfone Acid, perchloropentanesulfonic acid, perbromopentanesulfonic acid, periodopentanesulfonic acid, perfluorohexanesulfonic acid, perchlorohexanesulfonic acid, perbromohexanesulfonic acid, periodohexanesulfonic acid, perfluoroheptanesulfonic acid, Perchloroheptane sulfonic acid, perbromoheptane sulfonic acid, periodoheptane sulfonic acid, perfluorooctane sulfonic acid, perchlorooctane sulfonic acid, per Lomooctanesulfonic acid, periodooctanesulfonic acid, perfluorononanesulfonic acid, perchlorononanesulfonic acid, perbromononanesulfonic acid, periodononanesulfonic acid, perfluorodecanesulfonic acid, perchlorodecanesulfonic acid, perbromodecane Sulfonic acid, Periododecanesulfonic acid, Perfluoroundecanesulfonic acid, Perchloroundecanesulfonic acid, Perbromoundecanesulfonic acid, Periodoundecanesulfonic acid, Perfluorododecanesulfonic acid, Perchlorododecanesulfonic acid, Perbromododecanesulfonic acid , Periodododecanesulfonic acid, Perfluorotridecanesulfonic acid, Perchlorotridecanesulfonic acid, Perbromotridecanesulfonic acid, Periodotridecanesulfonic acid, -Fluorotetradecane sulfonic acid, perchlorotetradecane sulfonic acid, perbromotetradecane sulfonic acid, periodotetradecane sulfonic acid, perfluoropentadecane sulfonic acid, perchloropentadecane sulfonic acid, perbromopentadecane sulfonic acid, periodopentadecane sulfonic acid, perfluoro Haloalkyl sulfonic acids such as hexadecane sulfonic acid, perchlorohexadecane sulfonic acid, perbromohexadecane sulfonic acid, and periodohexadecane sulfonic acid, such as cyclopentane sulfonic acid, cycloalkyl sulfonic acid such as cyclohexane sulfonic acid, such as 2-fluorocyclopentane sulfone Acid, 2-chlorocyclopentanesulfonic acid, 2-bromocyclopentanesulfonic acid, 3-fluorocyclopentanesulfonic acid 3-chlorocyclopentanesulfonic acid, 3-bromocyclopentanesulfonic acid, 3,4-difluorocyclopentanesulfonic acid, 3,4-dichlorocyclopentanesulfonic acid, 3,4-dibromocyclopentanesulfonic acid, 4-fluorocyclohexane Sulfonic acid, 4-chlorocyclohexanesulfonic acid, 4-bromocyclohexanesulfonic acid, 4-iodocyclohexanesulfonic acid, 2,4-difluorocyclohexanesulfonic acid, 2,4-dichlorocyclohexanesulfonic acid, 2,4-dibromocyclohexanesulfonic acid 2,4-diiodocyclohexanesulfonic acid, 2,4,6-trifluorocyclohexanesulfonic acid, 2,4,6-trichlorocyclohexanesulfonic acid, 2,4,6-tribromocyclohexanesulfonic acid, 2,4, 6-triiodocyclohexanesulfonic acid, tetrafluorocyclohexanesulfonic acid, Halogenated cycloalkylsulfonic acid such as trachlorocyclohexanesulfonic acid, tetrabromocyclohexanesulfonic acid, tetraiodocyclohexanesulfonic acid, for example, arylsulfonic acid such as benzenesulfonic acid, naphthalenesulfonic acid, anthracenesulfonic acid, such as 2-fluorobenzenesulfone Acid, 3-fluorobenzenesulfonic acid, 4-fluorobenzenesulfonic acid, 2-chlorobenzenesulfonic acid, 3-chlorobenzenesulfonic acid, 4-chlorobenzenesulfonic acid, 2-bromobenzenesulfonic acid, 3-bromobenzenesulfonic acid, 4- Bromobenzenesulfonic acid, 2-iodobenzenesulfonic acid, 4-iodobenzenesulfonic acid, 2,4-difluorobenzenesulfonic acid, 2,6-difluorobenzenesulfonic acid, 2,4-dichlorobenzenesulfonic acid, 2,6- Dichlorobe Zensulfonic acid, 2,4-dibromobenzenesulfonic acid, 2,6-dibromobenzenesulfonic acid, 2,4-diiodobenzenesulfonic acid, 2,6-diiodobenzenesulfonic acid, 2,4,6-trifluorobenzene Sulfonic acid, 3,4,5-trifluorobenzenesulfonic acid, 2,4,6-trichlorobenzenesulfonic acid, 3,4,5-trichlorobenzenesulfonic acid, 2,4,6-tribromobenzenesulfonic acid, 3 , 4,5-Tribromobenzenesulfonic acid, 2,4,6-triiodobenzenesulfonic acid, 3,4,5-triiodobenzenesulfonic acid, pentafluorobenzenesulfonic acid, pentachlorobenzenesulfonic acid, pentabromobenzenesulfone Acid, pentaiodobenzenesulfonic acid, fluoronaphthalenesulfonic acid, chloronaphthalenesulfonic acid, bromonaphthalenesulfonic acid, iodonaphthalenesulfonic acid, fluoro Halogenated aromatic sulfonic acids such as anthracene sulfonic acid, chloroanthracene sulfonic acid, bromoanthracene sulfonic acid, iodoanthracene sulfonic acid, such as p-toluenesulfonic acid, 4-isopropylbenzenesulfonic acid, 3,5-bis (trimethyl) benzene Alkyl aromatic sulfonic acids such as sulfonic acid, 3,5-bis (isopropyl) benzenesulfonic acid, 2,4,6-tris (trimethyl) benzenesulfonic acid, 2,4,6-tris (isopropyl) benzenesulfonic acid, For example, 2-trifluoromethylbenzenesulfonic acid, 2-trichloromethylbenzenesulfonic acid, 2-tribromomethylbenzenesulfonic acid, 2-triiodomethylbenzenesulfonic acid, 3-trifluoromethylbenzenesulfonic acid, 3-trichloromethylbenzene Sulfonic acid, 3-tribromomethylbenzenesulfonic acid 3-triiodomethylbenzenesulfonic acid, 4-trifluoromethylbenzenesulfonic acid, 4-trichloromethylbenzenesulfonic acid, 4-tribromomethylbenzenesulfonic acid, 4-triiodomethylbenzenesulfonic acid, 2,6-bis ( (Trifluoromethyl) benzenesulfonic acid, 2,6-bis (trichloromethyl) benzenesulfonic acid, 2,6-bis (tribromomethyl) benzenesulfonic acid, 2,6-bis (triiodomethyl) benzenesulfonic acid, 3 , 5-bis (trifluoromethyl) benzenesulfonic acid, 3,5-bis (trichloromethyl) benzenesulfonic acid, 3,5-bis (tribromomethyl) benzenesulfonic acid, 3,5-bis (triiodomethyl) Examples thereof include halogenated alkyl aromatic sulfonic acids such as benzenesulfonic acid, and heterocyclic sulfonic acids such as pyridinesulfonic acid and pyrazinesulfonic acid.

  Preferred specific examples of the group represented by the general formula [3] include, for example, a diacetoxyiodo group, a dipropanoyloxyiodo group, a dibutanoyloxyiodo group, a diisobutanoyloxyiodo group, a divaleryloxyiodo group, Isovaleryloxyiodo group, dipivaloyloxyiodo group, dilauroyloxyiodo group, dipentanoyloxyiodo group, dihexanoyloxyiodo group, dicyclohexanoyloxyiodo group, dioctanoyloxyiodo group, Dinonanoyloxyiodo group, didecanoyloxyiodo group, dilauroyloxyiodo group, didodecanoyloxyiodo group, diundecanoyloxyiodo group, dipentadecanoyloxyiodo group, dihexadecanoyloxyiodo group, etc. Bis (aliphatic acyloxy) iodo groups such as diadamas Bis (alicyclic acyloxy) iodo groups such as tanoyloxyiodo group, for example bis (halogeno-substituted aliphatic acyloxy) iodo groups such as bis (trifluoroacetoxy) iodo group, bis (trifluoropropionyloxy) iodo group, for example Dibenzoyloxyiodo group, 1,3,5-tri-tert-butylbenzoyloxyiodo group, dinaphthoyloxyiodo group, diphenanthrenecarbonyloxyiodo group, difluorenecarbonyloxyiodo group, dipyrenecarbonyloxyiodo group, etc. Bis (aromatic acyloxy) iodine groups such as dialanyliodo group, diasparagyliodine group, diglycyliodine group, dihistidyliodine group, dileusyliodide group, dilysyliodine group, diisoleusyliodine group, divalyliodo group, diphenylalanyliodine group, An acyloxyiodo group derived from an amino-protected amino acid such as a prolyliodo group, a ditriprofyliodo group, a dityrosyliodo group (N-protecting group includes, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, a benzyloxycarbonyl group, 9-fluorenylmethylcarbonyl group, trichloroethylcarbonyl group, trimethylsilylethoxycarbonyl group, allyloxycarbonyl group, formyl group, trifluoroacetyl group, tosyl group, acetyl group, benzoyl group, phthaloyl group, etc.) such as hydroxy ( Mesyloxy) iodo group, hydroxy (benzenesulfonyloxy) iodo group, hydroxy (tosyloxy) iodo group, hydroxy (p-ethylbenzenesulfonyloxy) iodo group, hydroxy (p-propylbenzene) Sulfonyloxy) iodo group, hydroxy (p-butylbenzenesulfonyloxy) iodo group, hydroxy (p-pentylbenzenesulfonyloxy) iodo group, hydroxy (p-hexylbenzenesulfonyloxy) iodo group, hydroxy (p-heptylbenzenesulfonyloxy) Iodo group, hydroxy (p-octylbenzenesulfonyloxy) iodo group, hydroxy (p-nonylbenzenesulfonyloxy) iodo group, hydroxy (p-decylbenzenesulfonyloxy) iodo group, hydroxy (p-dodecylbenzenesulfonyloxy) iodo group , Hydroxy (trifluoromethanesulfonyloxy) iodo group, hydroxy (nonafluorobutanesulfonyloxy) iodo group, hydroxy (p-nitrobenzenesulfonyloxy) iodo group, hydroxy (2,4- Nitrobenzenesulfonyloxy) iodo groups, hydroxy (organosulfonyloxy) iodo groups such as hydroxy (camphorsulfonyloxy) iodo groups, such as methoxy (tosyloxy) iodine groups, ethoxy (tosyloxy) iodo groups, 1-menthyloxy (tosyloxy) iodo groups Alkoxy (organosulfonyloxy) iodo groups such as 2-tert-butylvinyliodo group, 2,2-methyl-tert-butylvinyliodo group, 2,2-phenyl-tert-butylvinyliodo group, 2-phenyl Vinyliodo group, 2,2-methylphenylvinyliodo group, 2,2-diphenylvinyliodo group, 2-methyl-1-propenyliodo group, 3-cyclopentyl-1-propenyliodo group, 3-cyclopentyl-2-methyl -1-propenyliodo group, 3-cyclopentyl-2-phenyl-1-propenyliodo group, 3-methoxy-1-propyl Penyl iodo group, 5-phenyl-1-pentenyl iodo group, 2-methyl-5-phenyl-1-pentenyl iodo group, 2,5-diphenyl-1-pentenyl iodo group, 5-chloro-1-pentenyl iodo group, 5 -Chloro-2-methyl-1-pentenyliodo group, 5-chloro-2-phenyl-1-pentenyliodo group, 5-cyano-1-pentenyliodo group, 5-cyano-2-methyl-1-pentenyliodo group 5-cyano-2-phenyl-1-pentenyliodo group, 1-hexenyliodo group, 2-methyl-1-hexenyliodo group, 2-phenyl-1-hexenyliodo group, 1-decenyliodo group, 2-methyl- 1-decenyl iodo group, 2-phenyl-1-decenyl iodo group, 5-methyl-1-hexenyl iodo group, 2,5-dimethyl-1-hexenyl iodo group, 5-methyl-2-phenyl-1-hexenyl iodo group, Alkenyliodo groups such as 2-benzenesulfonylvinyliodo group, for example 2-phenyl Tinyliodo, 2-phenylethynyliodo, p-tolyl-2-ethynyliodo, 2-trimethylsilylethynyliodo, 2-cyanoethynyliodo, 2-methoxycarbonylethynyliodo, 2-benzoylethynyliodo, 2 -Pivaloylethynyliodo group, 1-propynyliodo group, 3-methoxy-1-propynyliodo group, 4-tert-butyldimethylsilyloxy-1-butynyliodo group, 3,3-dimethyl-1-butynyliodo group, 1 Alkynyliodo groups such as -hexynyliodo group, 1-octynyliodo group, 1-dodecynyliodo group, 2-benzenesulfonylethynyliodo group, etc., among others, for example, diacetoxyiodo group, ditrifluoroacetyloxyiodo group, hydroxy (tosyloxy) Iodo group, hydroxy (mesyloxy) iodo group, 2-phenylethynyliodo Etc. are preferred, inter alia, for example diacetoxyiodo group, ditrifluoroacetic acetoxy iodo group, hydroxy (tosyloxy) iodo group are more preferable.

  Preferable specific examples of the group represented by the general formula [10] include substituents combining a cation part and an anion part. Specific examples of the cation part include, for example, phenyliodonium group, naphthyliodonium group, anthryl. Iodenyl group, phenanthryl iodonium group, fluorenyl iodonium group, spirobifluorenyl iodonium group, 4-chlorophenyl iodonium group, 4-bromophenyl iodonium group, o-tolyl iodonium group, m-tolyl iodonium group, p -Tolyliodonium group, 2-methoxyphenyliodonium group, 3-methoxyphenyliodonium group, o- (trimethylsilyl) phenyliodonium group, 2-thienyliodonium group, 3-thienyliodonium group, 2-benzothienyliodonium group, 3-benzo Thienyl iodonium group Examples include an imidazolyl iodonium group and a furyl iodonium group, and specific examples of the anion moiety include fluorides such as fluoride, chloride, bromide and iodide, for example, anions derived from sulfonic acids such as triflate, nonafluorobutane sulfonate, and tosylate. , Tetrafluoroborate, hexafluorophosphate, perchlorate, hydrogen sulfate and the like. Preferred combinations of the cation part and the anion part include, for example, p-tolyliodonium and triflate, p-tolyliodonium and tetrafluoroborate, p-tolyliodonium and hexafluorophosphate, phenyliodonium and triflate, phenyliodonium and tosylate, etc. Is mentioned.

  Preferable specific examples of the group represented by the general formula [13] include, for example, 1,1-methanedicarboxyiodo group, 1,2-ethanedicarboxyiodo group, 1,3-propanedicarboxyiodo group, 1,4 Cyclic diester groups derived from aliphatic dicarboxylic acids such as -butanedicarboxyiodo group, 1,5-pentanedicarboxyiodo group, 1,6-hexanedicarboxyiodo group, 1,7-heptanedicarboxyiodo group, for example 1, Cyclic diester groups derived from aliphatic acyl-substituted succinic acid such as 2-diacetoxyethanedicarboxyiodo group, 1,2-dipropionyloxyethanedicarboxyiodo group, such as 1,2-dibenzoyloxyethanedicarboxyiodo group, 1 Aromatic acyl-substituted succinic acid-derived cyclic diester groups such as 1,2-ditoluoyloxyethanedicarboxyiodo group, such as phthaloyloxyiodo group, isophthaloyl Examples thereof include cyclic diester groups derived from aromatic dicarboxylic acids such as oxyiodo groups. Among them, for example, 1,2-ethanedicarboxyiodo group, 1,2-diacetoxyethanedicarboxyiodo group, 1,2-dibenzoyloxyethane A carboxyiodo group, a phthaloyloxyiodo group and the like are preferable.

等が挙げられる。 Preferable specific examples of the ylide group represented by the general formula [15] include, for example,

Etc.

等が挙げられる。 Preferable specific examples of the ylide group represented by the general formula [16] include, for example,

Etc.

  Preferred examples of the group represented by the general formula [17] include, for example, 1,3,5,7-tetrakis- [4- (4- (3,5,7-tris (4-hydroxyiodophenyl) adamantyl) Cation moiety such as phenyl) iodo-μ-oxoiodo group and fluoride such as fluoride, chloride, bromide, iodide, anion derived from sulfonic acid such as triflate, nonafluorobutanesulfonate, tosylate, tetrafluoroborate, hexafluorophosphate And substituents combined with an anion moiety such as perchlorate, hydrogen sulfate, etc., among which, for example, 1,3,5,7-tetrakis- [4- (4- (3,5,7-tris ( 4-hydroxyiodophenyl) adamantyl) phenyl) iodo-μ-oxoiodo and tetrafluoroborate, 1,3,5,7-tetrakis- [4- (4- (3,5,7-tris (4-hydroxyiodo) Phenyl) adamantyl) phenyl) substituents combined iodo -μ- Okisoyodo and hexafluorophosphate are preferred.

As the hypervalent iodine compound represented by the general formula [1], for example, the general formula [20]

(Wherein Z, T, R ² , R ³ and q are the same as above), general formula [21]

(Wherein Z, T, R ¹² , Y ₁ and q are the same as above), general formula [22]

(Wherein Z, T, Y ₂ and q are the same as above), general formula [23]

(Wherein, Z, T and q are the same as above) and the like.

  Preferable specific examples of the hypervalent iodine compound represented by the general formula [20] include adamantane type compounds such as 1,3,5,7-tetrakis- (4- (diacetoxyiodo) phenyl) adamantane, 1,3,5,7-tetrakis- [4- (bis (trifluoroacetoxy) iodo) phenyl) adamantane, 1,3,5,7-tetrakis (4-((hydroxy) tosyloxyiodo) phenyl) adamantane, 1,3,5,7-tetrakis (4- (dipivaloyloxyiodo) phenyl) adamantane, 1,3,5,7-tetrakis (4- (dibenzoyloxyiodo) phenyl) adamantane, 1,3, 5,7-tetrakis (4- (di (1,3,5-tri-tert-butylbenzoyloxy) iodo) phenyl) adamantane, 1,3,5,7-tetrakis (4- (diadamantinoyloxyiodo) ) Phenyl) adamantane, 1,3,5,7-tetrakis- (4- (4-diacetoxyiodophenyl) phenyl) adamantane, 1 , 3,5,7-tetrakis- (4- (4-bis (trifluoroacetoxyiodophenyl) phenyl) adamantane, 1,3,5,7-tetrakis- (4- (4- (hydroxy) tosyloxyiodophenyl) ) Phenyl) adamantane, 1,3,5,7-tetrakis- (4- (4- (4-diacetoxyiodophenyl) phenyl) phenyl} adamantane, 1,3,5,7-tetrakis- (4- (4 -(4-Bis (trifluoroacetoxyiodophenyl) phenyl) phenyl} adamantane, 1,3,5,7-tetrakis-tetrakis- (4- (4- (4- (hydroxy) tosyloxyiodophenyl) phenyl) phenyl } Adamantane and the like, and examples of the methane type include tetrakis-4- (diacetoxyiodo) phenylmethane, tetrakis-4- (bis (trifluoroacetoxy) iodo) phenylmethane, tetrakis-4-((hydroxy) Tosyloxyiodo) phenylmethane, tetrakis-4- (dipivalo Luoxyiodo) phenylmethane, tetrakis-4-dibenzoyloxyiodo) phenylmethane, tetrakis-4- (di (1,3,5-tri-tert-butylbenzoyloxy) iodo) phenylmethane, tetrakis-4- (diadamant Tinoyloxyiodo) phenylmethane, tetrakis-4- (4-diacetoxyiodophenyl) phenylmethane, tetrakis-4- (4-bis (trifluoroacetoxyiodophenyl) phenylmethane, tetrakis-4- (4- (hydroxy ) Tosyloxyiodophenyl) phenylmethane, tetrakis-4- (4- (4-diacetoxyiodophenyl) phenyl) phenylmethane, tetrakis-4- (4- (4-bis (trifluoroacetoxyiodophenyl) phenyl) phenyl Methane, tetrakis-4- (4- (4- (hydroxy) tosyloxyiodophenyl) phenyl) phenylmethane and the like, among others, for example, 1,3,5,7 -Tetrakis- (4- (diacetoxyiodo) phenyl) adamantane, 1,3,5,7-tetrakis- (4- (ditrifluoroacetyloxyiodo) phenyl) adamantane, 1,3,5,7-tetrakis (4 -((Hydroxy) tosyloxyiodo) phenyl) adamantane, tetrakis-4- (diacetoxyiodo) phenylmethane, tetrakis-4- (ditrifluoroacetyloxyiodo) phenylmethane, tetrakis-4-((hydroxy) tosyloxyiodo ) Phenylmethane and the like are preferred.

Preferable specific examples of the hypervalent iodine compound represented by the general formula [21] include adamantane type compounds such as 1,3,5,7-tetrakis- (4- (phenyliodonium) phenyl) adamantane tetra ( Fluoride), 1,3,5,7-tetrakis- (4- (phenyliodonium) phenyl) adamantane tetra (chloride), 1,3,5,7-tetrakis- (4- (phenyliodonium) phenyl) adamantane tetra ( Bromide), 1,3,5,7-tetrakis- (4- (phenyliodonium) phenyl) adamantane tetra (iodide), 1,3,5,7-tetrakis- (4- (phenyliodonium) phenyl) adamantane tetra ( Tetrafluoroborate), 1,3,5,7-tetrakis- (4- (phenyliodonium) phenyl) adamantane tetra (hexafluorophosphate), 1,3,5,7-tetrakis- (4- (phenyliodonium) phenyl Ada N-tetra- (perchlorate), 1,3,5,7-tetrakis- (4- (phenyliodonium) phenyl) adamantane tetra (hydrogensulfate), 1,3,5,7-tetrakis- (4- (phenyliodonium) ) Phenyl) adamantane tetra (trifluoromethanesulfonate), 1,3,5,7-tetrakis- (4- (phenyliodonium) phenyl) adamantane tetra (nonafluorobutanesulfonate), 1,3,5,7-tetrakis- ( 4- (phenyliodonium) phenyl) adamantane tetra (p-toluenesulfonate), 1,3,5,7-tetrakis- (4- (4-tolyliodonium) phenyl) adamantane tetra (fluoride), 1,3,5, 7-tetrakis- (4- (4-tolyliodonium) phenyl) adamantane tetra (chloride), 1,3,5,7-tetrakis- (4- (4-tolyliodonium) phenyl) adamantane tetra (bromide), 1, 3,5,7-teto Kis- (4- (4-tolyliodonium) phenyl) adamantane tetra (iodide), 1,3,5,7-tetrakis- (4- (4-tolyliodonium) phenyl) adamantane tetra (tetrafluoroborate), 1, 3,5,7-tetrakis- (4- (4-tolyliodonium) phenyl) adamantane tetra (hexafluorophosphate), 1,3,5,7-tetrakis- (4- (4-tolyliodonium) phenyl) adamantane tetra (Perchlorate), 1,3,5,7-tetrakis- (4- (4-tolyliodonium) phenyl) adamantane tetra (hydrofence sulfate), 1,3,5,7-tetrakis- (4- (4 -Tolyliodonium) phenyl) adamantane tetra (trifluoromethanesulfonate), 1,3,5,7-tetrakis- (4- (4-tolyliodonium) phenyl) adamantane tetra (nonafluorobutanesulfonate), 1,3,5, 7-Tetrakis- (4- (4-Tolyliodoni ) Phenyl) adamantane tetra (p-toluenesulfonate), 1,3,5,7-tetrakis- (4- (4-biphenyliodonium) phenyl) adamantane tetra (fluoride), 1,3,5,7-tetrakis- (4- (4-biphenyliodonium) phenyl) adamantane tetra (chloride), 1,3,5,7-tetrakis- (4- (4-biphenyliodonium) phenyl) adamantane tetra (bromide), 1,3,5, 7-tetrakis- (4- (4-biphenyliodonium) phenyl) adamantane tetra (iodide), 1,3,5,7-tetrakis- (4- (4-biphenyliodonium) phenyl) adamantane tetra (tetrafluoroborate), 1,3,5,7-tetrakis- (4- (4-biphenyliodonium) phenyl) adamantane tetra (hexafluorophosphate), 1,3,5,7-tetrakis- (4- (4-biphenyliodonium) phenyl) Adamantane Tetra (Park Roller ), 1,3,5,7-tetrakis- (4- (4-biphenyliodonium) phenyl) adamantane tetra (hydrogen sulfate), 1,3,5,7-tetrakis- (4- (4-biphenyliodonium) Phenyl) adamantane tetra (trifluoromethanesulfonate), 1,3,5,7-tetrakis- (4- (4-biphenyliodonium) phenyl) adamantane tetra (nonafluorobutanesulfonate), 1,3,5,7-tetrakis- (4- (4-biphenyliodonium) phenyl) adamantane tetra (p-toluenesulfonate), 1,3,5,7-tetrakis- (4- (4-fluorenyliodonium) phenyl) adamantane tetra (fluoride), 1 , 3,5,7-Tetrakis- (4- (4-fluorenyliodonium) phenyl) adamantane tetra (chloride), 1,3,5,7-tetrakis- (4- (4-fluorenyliodonium) phenyl ) Adamantane tetra (bromide), 1,3,5,7- Trakis- (4- (4-fluorenyliodonium) phenyl) adamantane tetra (iodide), 1,3,5,7-tetrakis- (4- (4-fluorenyliodonium) phenyl) adamantane tetra (tetrafluoroborate ), 1,3,5,7-tetrakis- (4- (4-fluorenyliodonium) phenyl) adamantane tetra (hexafluorophosphate), 1,3,5,7-tetrakis- (4- (4-full Oleenyliodonium) phenyl) adamantane tetra (perchlorate), 1,3,5,7-tetrakis- (4- (4-fluorenyliodonium) phenyl) adamantane tetra (hydrogensulfate), 1,3,5, 7-Tetrakis- (4- (4-fluorenyliodonium) phenyl) adamantane tetra (trifluoromethanesulfonate), 1,3,5,7-tetrakis- (4- (4-fluorenyliodonium) phenyl) adamantane tetra (Nonafluorobutanesulfo Nate), 1,3,5,7-tetrakis- (4- (4-fluorenyliodonium) phenyl) adamantane tetra (p-toluenesulfonate), 1,3,5,7-tetrakis- (4- (2 -Phenylethynyliodonium) phenyl) adamantane tetra (fluoride), 1,3,5,7-tetrakis- (4- (2-phenylethynyliodonium) phenyl) adamantane tetra (chloride), 1,3,5,7-tetrakis -(4- (2-phenylethynyliodonium) phenyl) adamantane tetra (bromide), 1,3,5,7-tetrakis- (4- (2-phenylethynyliodonium) phenyl) adamantane tetra (iodide), 1,3 , 5,7-tetrakis- (4- (2-phenylethynyliodonium) phenyl) adamantane tetra (tetrafluoroborate), 1,3,5,7-tetrakis- (4- (2-phenylethynyliodonium) phenyl) adamantane Tetra (hexafluorophosphate ), 1,3,5,7-tetrakis- (4- (2-phenylethynyliodonium) phenyl) adamantane tetra (perchlorate), 1,3,5,7-tetrakis- (4- (2-phenylethynyliodonium) ) Phenyl) adamantane tetra (hydrogensulfate), 1,3,5,7-tetrakis- (4- (2-phenylethynyliodonium) phenyl) adamantane tetra (trifluoromethanesulfonate), 1,3,5,7-tetrakis -(4- (2-phenylethynyliodonium) phenyl) adamantane tetra (nonafluorobutanesulfonate), 1,3,5,7-tetrakis- (4- (2-phenylethynyliodonium) phenyl) adamantane tetra (p-toluene) Sulfonate), 1,3,5,7-tetrakis- (4- (4-tolyliodoniumphenyl) phenyl) adamantane tetra (trifluoromethanesulfonate), 1,3,5,7-tetrakis- (4- (4-tolyl) Iodonium Nyl) phenyl) adamantane tetra (trifluoromethanesulfonate), 1,3,5,7-tetrakis- (4- (4- (4-tolyliodoniumphenyl) phenyl) phenyl} adamantane tetra (trifluoromethanesulfonate), 1,3 , 5,7-tetrakis- (4- (4- (4-tolyliodoniumphenyl) phenyl) phenyl} adamantane tetra (trifluoromethanesulfonate) and the like, and examples of the methane type include tetrakis-4- (phenyl Iodonium) phenylmethane tetra (fluoride), tetrakis-4- (phenyliodonium) phenylmethane tetra (chloride), tetrakis-4- (phenyliodonium) phenylmethane tetra (bromide), tetrakis-4- (phenyliodonium) phenylmethane tetra (Iodide), tetrakis-4- (phenyliodonium) phenylmethane tet (Tetrafluoroborate), tetrakis-4- (phenyliodonium) phenylmethane tetra (hexafluorophosphate), tetrakis-4- (phenyliodonium) phenylmethane tetra (perchlorate), tetrakis-4- (phenyliodonium) phenylmethane tetra (Hydrogen sulfate), tetrakis-4- (phenyliodonium) phenylmethane tetra (trifluoromethanesulfonate), tetrakis-4- (phenyliodonium) phenylmethane tetra (nonafluorobutanesulfonate), tetrakis-4- (phenyliodonium) phenyl Methane tetra (p-toluenesulfonate), tetrakis-4- (4-tolyliodonium) phenylmethane tetra (fluoride), tetrakis-4- (4-tolyliodonium) phenylmethane tetra (chloride), tetrakis-4- (4- Ryliodonium) phenylmethane tetra (bromide), tetrakis-4- (4-tolyliodonium) phenylmethane tetra (iodide), tetrakis-4- (4-tolyliodonium) phenylmethane tetra (tetrafluoroborate), tetrakis-4- (4-Tolyliodonium) phenylmethane tetra (hexafluorophosphate), tetrakis-4- (4-tolyliodonium) phenylmethane tetra (perchlorate), tetrakis-4- (4-tolyliodonium) phenylmethane tetra (hydrofencel) Fate), tetrakis-4- (4-tolyliodonium) phenylmethane tetra (trifluoromethanesulfonate), tetrakis-4- (4-tolyliodonium) phenylmethane tetra (nonafluorobutanesulfonate), tetrakis-4- (4-tolyl) Iodonium) phenylmethane tetra (p-tolue) Sulfonate), tetrakis-4- (4-biphenyliodonium) phenylmethane tetra (fluoride), tetrakis-4- (4-biphenyliodonium) phenylmethane tetra (chloride), tetrakis-4- (4-biphenyliodonium) phenylmethane tetra (Bromide), tetrakis-4- (4-biphenyliodonium) phenylmethane tetra (iodide), tetrakis-4- (4-biphenyliodonium) phenylmethane tetra (tetrafluoroborate), tetrakis-4- (4-biphenyliodonium) Phenylmethane tetra (hexafluorophosphate), tetrakis-4- (4-biphenyliodonium) phenylmethane tetra (perchlorate), tetrakis-4- (4-biphenyliodonium) phenylmethane tetra (hydrogen sulfate), tetrakis-4- (4-Biphenyliodonium) Nylmethane tetra (trifluoromethanesulfonate), tetrakis-4- (4-biphenyliodonium) phenylmethane tetra (nonafluorobutanesulfonate), tetrakis-4- (4-biphenyliodonium) phenylmethane tetra (p-toluenesulfonate), tetrakis- 4- (4-Fluorenyliodonium) phenylmethane tetra (fluoride), tetrakis-4- (4-fluorenyliodonium) phenylmethane tetra (chloride), tetrakis-4- (4-fluorenyliodonium) phenylmethane Tetra (bromide), tetrakis-4- (4-fluorenyliodonium) phenylmethane tetra (iodide), tetrakis-4- (4-fluorenyliodonium) phenylmethane tetra (tetrafluoroborate), tetrakis-4- ( 4-Fluorenyliodonium) phenylmethane tetra (hexaph Fluorophosphate), tetrakis-4- (4-fluorenyliodonium) phenylmethane tetra (perchlorate), tetrakis-4- (4-fluorenyliodonium) phenylmethane tetra (hydrogensulfate), tetrakis-4- (4-Fluorenyliodonium) phenylmethane tetra (trifluoromethanesulfonate), tetrakis-4- (4-fluorenyliodonium) phenylmethane tetra (nonafluorobutanesulfonate), tetrakis-4- (4-fluorenyliodonium ) Phenylmethane tetra (p-toluenesulfonate), tetrakis-4- (2-phenylethynyliodonium) phenylmethane tetra (fluoride), tetrakis-4- (2-phenylethynyliodonium) phenylmethane tetra (chloride), tetrakis-4 -(2-Phenylethynyliodonium) phenylmethane Tora (bromide), tetrakis-4- (2-phenylethynyliodonium) phenylmethane tetra (iodide), tetrakis-4- (2-phenylethynyliodonium) phenylmethane tetra (tetrafluoroborate), tetrakis-4- (2- Phenylethynyliodonium) phenylmethane tetra (hexafluorophosphate), tetrakis-4- (2-phenylethynyliodonium) phenylmethane tetra (perchlorate), tetrakis-4- (2-phenylethynyliodonium) phenylmethane tetra (hydrogen sulfate) ), Tetrakis-4- (2-phenylethynyliodonium) phenylmethane tetra (trifluoromethanesulfonate), tetrakis-4- (2-phenylethynyliodonium) phenylmethane tetra (nonafluorobutanesulfonate), tetrakis-4- (2- Phenyleth Ruiodonium) phenylmethane tetra (p-toluenesulfonate), tetrakis-4- (4-tolyliodoniumphenyl) phenylmethane tetra (trifluoromethanesulfonate), tetrakis-4- (4-tolyliodoniumphenyl) phenylmethane tetra (trifluoromethane Sulfonate), tetrakis-4- (4- (4-tolyliodoniumphenyl) phenyl) phenylmethane tetra (trifluoromethanesulfonate), tetrakis-4- (4- (4-tolyliodoniumphenyl) phenyl) phenylmethane tetra (trifluoromethane Among them, for example, 1,3,5,7-tetrakis- (4- (4-tolyliodonium) phenyl) adamantane tetra (trifluoromethanesulfonate), 1,3,5,7-tetrakis- ( 4- (Phenyliodonium) phenyl) adamantane tetra (trifluoro Tansulfonate), 1,3,5,7-tetrakis- (4- (2-phenylethynyliodonium) phenyl) adamantane tetra (tetrafluoroborate) and the like are preferred, for example, 1,3,5,7-tetrakis -(4- (4-Tolyliodonium) phenyl) adamantane tetra (trifluoromethanesulfonate), 1,3,5,7-tetrakis- (4- (phenyliodonium) phenyl) adamantane tetra (trifluoromethanesulfonate) and the like are more preferable .

  Preferable specific examples of the hypervalent iodine compound represented by the general formula [22] include adamantane type compounds such as 1,3,5,7-tetrakis- (4- (4- (3,5,7 -Tris (4-hydroxyiodophenyl) adamantyl) phenyl) iodo-μ-oxoiodophenyl) adamantane Icosakis (fluoride), 1,3,5,7-tetrakis- (4- (4- (3,5,7- Tris (4-hydroxyiodophenyl) adamantyl) phenyl) iodo-μ-oxoiodophenyl) adamantane Icosakis (chloride), 1,3,5,7-tetrakis- (4- (4- (3,5,7-tris) (4-Hydroxyiodophenyl) adamantyl) phenyl) iodo-μ-oxoiodophenyl) adamantane icosakis (bromide), 1,3,5,7-tetrakis- (4- (4- (3,5,7-tris ( 4-hydroxyiodophenyl) adamantyl) phenyl) iodo-μ-oxoiodophenyl) adaman Nikosakis (iodide), 1,3,5,7-tetrakis- (4- (4- (3,5,7-tris (4-hydroxyiodophenyl) adamantyl) phenyl) iodo-μ-oxoiodophenyl) adamantane Icosakis (tetrafluoroborate), 1,3,5,7-tetrakis- (4- (4- (3,5,7-tris (4-hydroxyiodophenyl) adamantyl) phenyl) iodo-μ-oxoiodophenyl) Adamantane Icosakis (hexafluorophosphate), 1,3,5,7-tetrakis- (4- (4- (3,5,7-tris (4-hydroxyiodophenyl) adamantyl) phenyl) iodo-μ-oxoiodophenyl ) Adamantane Icosakis (Perchlorate), 1,3,5,7-Tetrakis- (4- (4- (3,5,7-Tris (4-hydroxyiodophenyl) adamantyl) phenyl) iodo-μ-oxoiodophenyl ) Adamantane Icosakis (Hydrogen Sulfate), 1,3, 5,7-tetrakis- (4- (4- (3,5,7-tris (4-hydroxyiodophenyl) adamantyl) phenyl) iodo-μ-oxoiodophenyl) adamantan icosakis (triflate), 1,3, 5,7-tetrakis- (4- (4- (3,5,7-tris (4-hydroxyiodophenyl) adamantyl) phenyl) iodo-μ-oxoiodophenyl) adamantane icosakis (nonafluorobutanesulfonate), 1, 3,5,7-tetrakis- (4- (4- (3,5,7-tris (4-hydroxyiodophenyl) adamantyl) phenyl) iodo-μ-oxoiodophenyl) adamantan icosakis (tosylate) Examples of the methane type include tetrakis- (4- (4- (3,5,7-tris (4-hydroxyiodophenyl) methyl) phenyl) iodo-μ-oxoiodophenyl) methane icosakis (fluoride), Tetrakis- (4- (4- (3,5,7-tris (4-hydride Roxyiodophenyl) methyl) phenyl) iodo-μ-oxoiodophenyl) methane Icosakis (chloride), tetrakis- (4- (4- (3,5,7-tris (4-hydroxyiodophenyl) methyl) phenyl) iodo -μ-oxoiodophenyl) methane icosakis (bromide), tetrakis- (4- (4- (3,5,7-tris (4-hydroxyiodophenyl) methyl) phenyl) iodo-μ-oxoiodophenyl) methane icosakis (Iodide), tetrakis- (4- (4- (3,5,7-tris (4-hydroxyiodophenyl) methyl) phenyl) iodo-μ-oxoiodophenyl) methane icosakis (tetrafluoroborate), tetrakis- ( 4- (4- (3,5,7-tris (4-hydroxyiodophenyl) methyl) phenyl) iodo-μ-oxoiodophenyl) methane icosakis (hexafluorophosphate), tetrakis- (4- (4- (3 , 5,7-G (4-Hydroxyiodophenyl) methyl) phenyl) iodo-μ-oxoiodophenyl) methane Icosakis (Perchlorate), Tetrakis- (4- (4- (3,5,7-Tris (4-hydroxyiodophenyl)) Methyl) phenyl) iodo-μ-oxoiodophenyl) methane icosakis (hydrogen sulfate), tetrakis- (4- (4- (3,5,7-tris (4-hydroxyiodophenyl) methyl) phenyl) iodo-μ -Oxoiodophenyl) methane icosakis (triflate), tetrakis- (4- (4- (3,5,7-tris (4-hydroxyiodophenyl) methyl) phenyl) iodo-μ-oxoiodophenyl) methane icosakis ( Nonafluorobutanesulfonate), tetrakis- (4- (4- (3,5,7-tris (4-hydroxyiodophenyl) methyl) phenyl) iodo-μ-oxoiodophenyl) methane icosakis (tosylate) Tetrakis- (4- (4- (4- (3,5,7-tris (4-hydroxyiodophenyl) methyl) phenyl) iodo-μ-oxoiodophenyl) phenyl) methane icosakis (tetrafluoroborate), tetrakis- (4- (4- (4- (3,5,7-tris (4-hydroxyiodophenyl) methyl) phenyl) iodo-μ-oxoiodophenyl) phenyl) methane icosakis (hexafluorophosphate), tetrakis- (4 -(4- (4- (4- (3,5,7-tris (4-hydroxyiodophenyl) methyl) phenyl) iodo-μ-oxoiodophenyl) phenyl) phenyl) methane icosakis (tetrafluoroborate), tetrakis -(4- (4- (4- (4- (3,5,7-tris (4-hydroxyiodophenyl) methyl) phenyl) iodo-μ-oxoiodophenyl) phenyl) phenyl) methane icosakis (hexafluorophosphate ) Etc., among others 1,3,5,7-tetrakis- (4- (4- (3,5,7-tris (4-hydroxyiodophenyl) adamantyl) phenyl) iodo-μ-oxoiodophenyl) adamantan icosakis (tetrafluoroborate) 1,3,5,7-tetrakis- (4- (4- (3,5,7-tris (4-hydroxyiodophenyl) adamantyl) phenyl) iodo-μ-oxoiodophenyl) adamantane icosakis (hexafluorophosphate Etc.) are preferred.

  Preferable specific examples of the hypervalent iodine compound represented by the general formula [23] include 1,3,5,7-tetrakis- (4-iodosylphenyl) adamantane, tetrakis- (4-iodosylphenyl) methane, for example. 1,3,5,7-tetrakis- (4- (4-iodosylphenyl) phenyl) adamantane, tetrakis- (4- (4-iodosylphenyl) phenyl) methane, tetrakis- (4- (4- ( 4-iodosylphenyl) phenyl) phenyl) adamantane, tetrakis- (4- (4- (4-iodosylphenyl) phenyl) phenyl) methane, etc., among which 1,3,5,7-tetrakis- ( 4-Iodosylphenyl) adamantane is preferred.

The hypervalent iodine compound represented by the general formula [1] can be produced, for example, as follows. Here, <1> tetrakis- (4-diacetoxyiodo) phenyl [diacetate], <2> tetrakis- (4- (hydroxy) tosyloxyiodo) phenyl [hydroxytosyloxy], <3> tetrakis- (4- (4-Tolyliodonium) phenyl) (iodonium), <4> tetrakis- (4- (4-iodosyl) phenyl) (iodosyl) and <5> Z (Ph (I ⁺ -OI ⁺ This will be described below by taking -PhZ (PhI ⁺ -O) ₃ ) nH} ₄ [μ oxo] as an example.

<1> Synthesis of diacetate

(In the formula, Z, T and q are the same as above.)
* AcOH = CH ₃ COOH, AcO = acetoxy

That is, conventional methods (for example, H. Newman, Synthesis, p.692 (1972), VRReichert, LJMathias, Macromolecules, 27, p.7015 (1994), LJMathias, VRReichert, AVGMuir, Chem. Mater., 5, p.4) (1993), D.Su, FMMenger, Tetrahedron Letter, 38, p.1485 (1997), etc.) 1 mol of the iodine compound represented by the general formula [24] is added to an appropriate solvent (for example, methylene chloride, dichloroethane). Halogenated hydrocarbons such as chloroform, hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene and toluene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone such as ethyl ether and dimethoxy Ethers such as ethane, tetrahydrofuran, 1,4-dioxane, for example, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, acetonite In this case, it is dissolved or suspended in an aqueous solution, an excess amount of acetic acid is added to the iodine body, and then 8 to 12 moles relative to the iodine body. After adding an oxidizing agent such as mCPBA (= m-chloroperoxybenzoic acid), hydrogen peroxide, sodium perborate (NaBO ₃ ), the mixture is stirred at 15 to 40 ° C. for 6 to 24 hours, and then treated according to a conventional method. By doing this, the diacetate body represented by the general formula [25] according to the present invention is obtained.

<2> Synthesis of hydroxytosyloxy compound

(In the formula, Z, T and q are the same as above.)
* TsOH = p-toluenesulfonic acid, TsO = p-toluenesulfonyloxy (tosyloxy)

That is, 4 to 20 times moles of tosylic acid monohydrate (TsOH.H ₂ O) or tosylic acid and water with respect to 1 mole of the diacetate compound represented by the above general formula [25] at room temperature in a nitrogen atmosphere And a suitable solvent (for example, halogenated hydrocarbons such as methylene chloride, dichloroethane, and chloroform, hydrocarbons such as cyclohexane, aromatic hydrocarbons such as benzene and toluene, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Ketones such as ethyl ether, dimethoxyethane, 1,4-dioxane, tetrahydrofuran, etc., amides such as N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, etc. Acetonitrile is preferred) and dissolved or suspended in the above general formula [ 5] After adding the diacetate represented by 5] and reacting with stirring at 15 to 40 ° C. for 5 hours, the hydroxytosyloxy compound represented by the general formula [26] according to the present invention is obtained by treatment according to a conventional method. .

<3> Synthesis of iodonium bodies

(In the formula, Z, T and q are the same as above.)
_{※ TfOH = trifluorometanesulfonic acid (CF 3} SO 3 H), TfO - = triflate (CF 3 SO 3 -)

  That is, 1 mol of a diacetate represented by the above general formula [25] is added to a suitable solvent (for example, halogenated hydrocarbons such as methylene chloride, dichloroethane and chloroform, for example, hydrocarbon such as cyclohexane) in a nitrogen atmosphere at 0 ° C. Such as aromatic hydrocarbons such as benzene and toluene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethers such as ethyl ether, dimethoxyethane, 1,4-dioxane, such as N, N Amides such as dimethylformamide and N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, etc., particularly acetonitrile is preferred) and is 4 to 20 times the diacetate represented by the above general formula [25]. Moles, preferably 8 moles of trifluoromethanesulfur The phosphate was added, by one hour of stirring the reaction at room temperature. After completion of the reaction, the obtained reaction solution is cooled to 0 ° C., 6 to 8 times mol of toluene is added to the diacetate, and stirred at room temperature for 8 hours, and then treated according to a conventional method. A tolyliodonium salt represented by the general formula [27] according to the present invention is obtained.

<4> Synthesis of iodosyl

(In the formula, Z, T and q are the same as above.)

  That is, a basic aqueous solution such as sodium hydroxide, lithium hydroxide, potassium hydroxide, cesium hydroxide and the like in 10 to 300 times mole of the diacetate body per 1 mole of the diacetate body represented by the general formula [25]. And stirred for 1 to 3 hours at room temperature. After completion of the reaction, the iodosil compound represented by the general formula [23] according to the present invention is obtained by processing according to a conventional method.

<5> μ oxo form (when n = 1)

(In the formula, Z, Y ₂ , T and q are the same as above.)
That is, 1 mol of the diacetate represented by the above general formula [25] is added to a suitable solvent (for example, halogenated hydrocarbons such as methylene chloride, dichloroethane, chloroform, etc., hydrocarbons such as cyclohexane, eg benzene, toluene, etc. Aromatic hydrocarbons such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ketones such as cyclohexanone, such as ethers such as ethyl ether, dimethoxyethane, 1,4-dioxane, such as N, N-dimethylformamide, N, N- Amides such as dimethylacetamide, acetonitrile, dimethyl sulfoxide, etc., particularly preferred are halogenated hydrocarbons.) 5 equivalents of HY ₂ aqueous solution is added to the diacetate, and 0.5 to 5 at 15 to 40 ° C. Stir for 3 hours. After completion of the reaction, the μ oxo form (n = 1) represented by the general formula [28] according to the present invention is obtained by processing according to a conventional method.

  The hypervalent iodine compound represented by the general formula [1] according to the present invention is used as various oxidizing reagents such as an oxidation reaction of alcohols and phenols, an α-tosiloxylation reaction of ketones, and an oxidative biaryl coupling reaction. For example, it can be used as a selective reaction reagent such as a selective α-tosiloxylation reaction of ketones.

Further, when the hypervalent iodine compound of the present invention is used as a reaction reagent as described above, since the iodine body, which is a precursor of the hypervalent iodine compound, is extremely hardly soluble in methanol, the reaction product is made of methanol. By extraction, the oxidizing reagent can be easily separated and recovered as an iodine body. This reuse process is shown below (exemplified as a hypervalent compound according to the present invention is a diacetate form (adamantane type)).

  The hypervalent iodine compound of the present invention is reused due to the presence of the benzylic proton in the polystyrene chain, which is possessed by the conventional polymer reagent, that is, when the reagent is re-oxidized from the iodine body to regenerate the reaction reagent. The iodine compound can be efficiently recovered and reused without the problem that the deterioration of the polymer proceeds little by little.

  Furthermore, since the hypervalent iodine compound of the present invention has a tetrahedral structure in which the four reaction sites do not interfere with each other, the reaction sites are buried in, for example, the polymer chain that the conventional polymer reagent had. It has high reactivity equivalent to or higher than that of the monomer reagent without problems such as inefficiency and need of an excess reagent, and difficulty in keeping the reaction site introduction efficiency constant.

  Hereinafter, the present invention will be described in more detail with reference to Examples, Experimental Examples, Reference Examples, and Comparative Examples, but the present invention is not limited thereto.

Reference Example 1. Synthesis of 1,3,5,7-tetraphenyladamantane

* PhH = benzene, t-BuBr = tert-butylbromide
According to a conventional method (for example, see H. Newman, Synthesis, p.692 (1972), etc.) in a nitrogen atmosphere, 5.0 g of 1-bromoadamantane and 5.4 mL (2.0 equiv.) Of tert-butyl bromide in 50 mL of benzene Was added and dissolved, and 250 mg of aluminum chloride (AlCl ₃ ) was added to the resulting benzene solution, and immediately refluxed at 100 to 110 ° C. for 2 hours. After completion of the reaction, 100 mL of ice water and 50 mL of diethyl ether were added to the resulting reaction solution, and the remaining crude crystals were collected by filtration and washed with water and diethyl ether. Next, 150 mL of benzene was added to the obtained crude crystals, heated, filtered hot at 70-80 ° C. (additionally diethyl ether if benzene solidifies), and then washed with heated benzene. Then, 6.9 g of the desired product was obtained as a white solid (yield: 70%).

Reference Example 2. Synthesis of 1,3,5,7-tetrakis (4-iodophenyl) adamantane [iodine (adamantane type)]

* PIFA = Phenyliodine (III) bis (trifluoroacetate) = PhI (OCOCF ₃ ) ₂
Chloroform (CHCl ₃ ) 25 according to conventional methods (eg, VRReichert, LJMathias, Macromolecules, 27, p. 7015 (1994), LJMathias, VRReichert, AVGMuir, Chem. Mater., 5, p. 4 (1993), etc.) After 6.9 g of tetraphenyladamantane was dissolved in mL, 7.96 g (2.0 equiv.) of iodine and 16.2 mL (2.4 equiv.) of PIFA were added, and the mixture was stirred at 15 to 30 ° C. overnight. After completion of the reaction, 25 mL of a saturated aqueous sodium thiosulfate solution and 25 mL of a saturated aqueous sodium bicarbonate solution were added to the resulting reaction solution, and extracted twice with 100 mL of chloroform. The obtained organic layer was washed with 25 mL of saturated aqueous sodium hydrogen carbonate solution, 25 mL of water and 50 mL of saturated aqueous sodium chloride solution, dried and concentrated to obtain crude crystals. The obtained crude crystals were recrystallized from a chloroform / methanol mixed solvent (= 10/1) to obtain 12.8 g of the desired product as colorless needle crystals (yield: 86%).

Example 1. Synthesis of 1,3,5,7-tetrakis- (4- (diacetoxyiodo) phenyl) adamantane [diacetate I (adamantane type)]

1.416 g of 1,3,5,7-tetrakis (4-iodophenyl) adamantane obtained in Reference Example 2 was added and dissolved in 150 mL of dichloromethane (CH ₂ Cl ₂ ) and 150 mL of acetic acid, and then further m-chloro. Perbenzoic acid (mCPBA) 3.12 g (12equiv.) Was added and the reaction was allowed to stir at 15-30 ° C. for 13 hours. After completion of the reaction, the resulting reaction solution was filtered to remove insoluble matters. Only dichloromethane was distilled off under reduced pressure, and 350 mL of n-hexane was added to the concentrated solution for crystallization. The supernatant was removed by decantation, n-hexane was further added to the obtained crude crystals, and this operation was repeated twice. Further, 20 mL of diethyl ether was added, the target product was crystallized, the supernatant was removed by decantation, the crude crystals were collected by filtration, washed with n-hexane and diethyl ether, dried, acetic acid / methylene chloride / Recrystallization from a hexane mixed solvent (= 1/1/1) gave 2.065 g of the desired product as colorless crystals (yield: 97.2%).
Physical property data:
mp 195-196 ° C (from AcOH-CH ₂ Cl ₂ / n-Hexane).
¹ H-NMR (CDCl ₃ , 300 MHz): δ8.09 (d, J = 8.4 Hz, 8H), 7.56 (d, J = 8.4 Hz, 8H), 2.20 (s, 12H), 2.01 (s, 24H) .
¹³ C-NMR (CDCl ₃ , 75 MHz): δ176.5, 151.9, 135.2, 127.7, 119.5, 46.4, 39.6, 20.4.
High resolution ESI mass (in MeOH): m / z 1422.87845 (Ad (PhI (OAc) ₂ ) ₃ (PhI ⁺ (OAc) O) / H ₂ O / MeOH).

Example 2. Synthesis of 1,3,5,7-tetrakis- (4- (hydroxy) tosyloxyiodo) phenyl) adamantane [hydroxytosyloxy I (adamantane type)]

Under a nitrogen atmosphere, diacetate I obtained in Example 1 (into a solution obtained by adding 537 mg of tosylic acid monohydrate (TsOH.H ₂ O) in 4.2 mL of anhydrous acetonitrile (dryCH ₃ CN) was dissolved. Adamantane type) 500 mg (0.353 mmol) was added, and the mixture was stirred at room temperature for 5 hours. After completion of the reaction, 10 mL of acetonitrile and 10 mL of diethyl ether were added to the resulting reaction solution and stirred for 10 minutes, followed by filtration to obtain crude crystals. The obtained crude crystals were washed with 20 mL of diethyl ether and then dried to obtain 564 mg of the desired product as pale yellow crystals (94%).
Physical property data:
mp 183-190 ° C
¹ H-NMR (CDCl ₃ / CF ₃ CO ₂ H (= 10/1), 270 MHz): δ8.25 (d, J = 8.9 Hz, 8H), 7.70 (d, J = 8.9 Hz, 8H), 7.65 (d, J = 8.4Hz, 8H), 7.26 (d, J = 8.1Hz, 8H), 2.38 (s, 12H), 2.26 (s, 12H).
¹³ C-NMR (CDCl ₃ / CF ₃ CO ₂ H (= 10/1), 75 MHz): δ 154.2, 144.5, 135.9, 135.1, 129.8, 129.0, 126.3, 121.1, 45.8, 39.9, 21.4.
High resolution ESI mass (in MeOH): m / z 1581.96131 (Ad (PhI (OTs) OMe) ₃ (PhI ⁺ OMe))

Example 3 Synthesis of 1,3,5,7-tetrakis- (4- (4-tolyliodonium) phenyl) adamantane [Iodonium Form I (adamantane type)]

Diacetate I (adamantane type) obtained in Example 2 (212.4 mg, 0.15 mmol) was added and dissolved in 3 mL of anhydrous dichloromethane at 0 ° C. under a nitrogen atmosphere, and then trifluoromethanesulfonic acid (TfOH) 106.2 μl (1.20 mmol) was slowly added, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the resulting reaction solution was cooled to 0 ° C., 127.8 μl (1.2 mmol) of anhydrous toluene was added, and the mixture was stirred at room temperature for 8 hours. Dichloromethane was distilled off under reduced pressure while stirring the resulting solution, and 15 mL of diethyl ether was added to crystallize the desired product. The obtained crystallized product was collected by filtration under reduced pressure, washed with diethyl ether and dried to give 248 mg of the desired product as colorless crystals (87%).
Physical property data:
mp 186 ~ 190 ° C
¹ H-NMR (CD ₃ CN, 270 MHz): δ8.00 (d, J = 8.6 Hz, 8H), 7.94 (d, J = 8.4 Hz, 8H), 7.62 (d, J = 8.6 Hz, 8H), 7.32 (d, J = 8.1Hz, 8H), 2.37 (s, 12H), 2.04 (s, 12H).
¹³ C-NMR (CD ₃ CN, 67.8 MHz): δ154.6, 145.1, 136.2, 136.1, 133.8, 130.3, 124.0, 112.0, 110.9, 45.8, 40.6, 21.4.
High resolution ESI mass (in CH ₃ CN): m / z 1755.88990 (C ₆₂ H ₁₅ I ₄ ⁺ / 3 (OSO ₂ CF ₃ )) (3OSO ₂ CF ₃ ).

Example 4 Synthesis of tetrakis-4- (diacetoxyiodo) phenylmethane [diacetate II (methane type)]

Starting from trityl chloride as a starting material, 852.5 mg (1.03 mmol) of tetra (iodophenyl) methane synthesized by a conventional method (see, for example, D.Su, FMMenger, Tetrahedron Lett., 38, p.1485 (1997)). After dissolving in 100 mL of dichloromethane, 100 mL of acetic acid (AcOH) and 2.142 g (12.41 mmol) of m-chloroperbenzoic acid (mCPBA) were added, and the reaction was stirred at 15-30 ° C. for 48 hours. After completion of the reaction, the obtained reaction solution was filtered, and only dichloromethane was distilled off under reduced pressure. 300 mL of n-hexane was added to the resulting concentrated solution for crystallization, and the supernatant was removed by decantation. N-Hexane was further added to the obtained crude crystals, and the same operation was repeated twice. The obtained crude crystals were washed with n-hexane and dried under reduced pressure to obtain 1.220 g of the desired product as colorless crystals (91.4%).
Physical property data:
mp (decomp.) 200 ° C (from AcOH / n-Hexane).
¹ H-NMR (CDCl ₃ , 300 MHz): δ 8.04 (d, J = 8.4 Hz, 8H), 7.32 (d, J = 8.7 Hz, 8H), 2.05 (s, 24H).
¹³ C-NMR (CDCl ₃ , 67.8 MHz): δ 176.4, 147.5. 134.7, 132.9, 119.7, 65.0, 20.6.
High resolution ESI mass (in MeOH): m / z 1302.78679 (C (PhI (OAc) ₂ ) ₃ (PhI ⁺ (OAc) (OMe) OH) / H ₂ O)

Example 5 Synthesis of 1,3,5,7-tetrakis- (4-bis (trifluoroacetoxyiodo) phenyl) adamantane [bistrifluoroacetate I (adamantane type)]

* TFA = trifluoroacetic acid
To 8 mL of chloroform, diacetate I obtained in Example 1 (adamantane type) 495.8 mg (0.35 mmol) was added and dissolved, and 8 mL (83.1 mmol) of trifluoroacetic acid (TFA) was added at room temperature. And stirred for 1.5 hours. After the reaction is complete. While stirring the resulting reaction liquid, chloroform was distilled off under reduced pressure, and crystallization was performed from a hexane / diethyl ether mixed solvent (= 10/1). The obtained crude crystals were decanted twice with 30 mL of the same mixed solvent, washed, and then collected by filtration to obtain 578.7 mg of the desired product as pale yellow crystals (yield: 89%).
Physical property data:
mp 196-203 ℃
¹ H-NMR (CDCl ₃ / CF ₃ CO ₂ H (= 10/1)) 300 MHz: δ8.24 (d, J = 8.7Hz, 8H), 7.73 (d, J = 8.7Hz, 8H), 2.30 ( s, 12H)
¹³ C-NMR (CDCl ₃ / CF ₃ CO ₂ H (= 10/1)) 300 Hz: δ166.0, 154.3, 136.0, 129.2, 120.7, 116.8, 46.0, 40.1

Example 6 Synthesis of 1,3,5,7-tetrakis- (4-iodosylphenyl) adamantane [iodosyl I (adamantane type)]

20 mL of 3N NaOHaq. Was slowly added to 283.3 mg (0.2 mmol) of acetate I (adamantane type) obtained in Example 1, and the mixture was stirred at room temperature for 1.5 hours. After completion of the reaction, the resulting reaction solution was filtered, washed twice with 20 mL of water and 20 mL of diethyl ether, and then dried to obtain 160 mg of the desired product as pale yellow crystals (yield: 79%).
Physical property data:
¹ H-NMR (DMSO-d6) 270 MHz: δ7.63 (d, J = 7.8 Hz, 8H), 7.30 (d, J = 7.6 Hz, 8H), 1.95 (s, 12H)

Example 7. 1,3,5,7-tetrakis- (4- (4- (3,5,7-tris (4-hydroxyiodophenyl) adamantyl) phenyl) iodo-μ-oxoiodophenyl) adamantan icosakis ( Synthesis of tetrafluoroborate) [μ oxo isomer I (adamantane type)]

In 0.5 mL of chloroform, 70.8 mg (0.05 mmol) of diacetate I (adamantane type) obtained in Example 1 was added and dissolved, and then 5 equivalents of tetrafluoroboric acid aqueous solution was added to the acetate. Slowly added. Immediately yellowing. After 1 hour, chloroform in the obtained reaction solution was distilled off under reduced pressure, and the formation of the target product was confirmed by NMR measurement.
Physical property data:
¹ H-NMR (DMSO-d6) 270MHz: δ8.17 (d, J = 8.4Hz, 8H), 7.83 (d, J = 8.4Hz, 8H), 2.16 (s, 12H)

Example 8. 1,3,5,7-Tetrakis- (4- (4- (3,5,7-tris (4-hydroxyiodophenyl) adamantyl) phenyl) iodo-μ-oxoiodophenyl) adamantane Icosakis ( Hexafluorophosphate) [μ-oxo I (adamantane type)]

Instead of the tetrafluoroboric acid aqueous solution used in Example 7, the same operation as in Example 7 was performed except that a hexafluorophosphoric acid aqueous solution was used, and the production of the target product was confirmed by NMR measurement.
Physical property data:
¹ H-NMR (DMSO-d6) 270 MHz: δ8.25-8.00 (m, 8H), 7.90-7.65 (m, 8H), 2.25-2.00 (m, 12H)

Example 9 Synthesis of tetrakis-4-bis (trifluoroacetoxyiodo) phenylmethane [bistrifluoroacetate II (methane type)]

Under nitrogen atmosphere, 38.9 mL of diacetate II (methane type) 388.9 mg (0.30 mmol) obtained in Example 4 was added to 3 mL of chloroform, and 3 mL of trifluoroacetic acid (TFA) was added to the dissolved solution at room temperature. And stirred for 1.5 hours. After completion of the reaction, chloroform was distilled off under reduced pressure while stirring the resulting reaction solution, and crystallized from a hexane / diethyl ether mixed solvent (= 10/1). The obtained crude crystals were washed by decanting twice with 30 mL of the same mixed solvent, and then collected by filtration to obtain 479.9 mg of the desired product as colorless crystals (yield: 93%).
Physical property data:
mp 158-160 ℃
¹ H-NMR (CDCl ₃ / CF ₃ CO ₂ H (= 10/1)) 300 MHz: δ8.19 (d, J = 9.9 Hz, 8H), 7.41 (d, J = 9.6 Hz, 8H).
F-NMR (CDCl ₃ / CF ₃ CO ₂ H (= 10/1)): δ-74.47 ppm (s, 24F; OCOCF ₃ ).
IR (KBr): 1770.5 s, 1681.8 s, 1180.4 s, 912.3 w cm- ¹ .

Example 10 Synthesis of tetrakis-4- (hydroxy) tosyloxyiodo) phenylmethane [hydroxytosyloxy II (methane type)]

Example 4 To a solution obtained by adding and dissolving 380.4 mg (2.00 mmol, 8 eq.) Of tosylic acid monohydrate (TsOH · H ₂ O) in 5.0 mL of anhydrous acetonitrile (dryCH ₃ CN) under nitrogen atmosphere Then, 324.1 mg (0.25 mmol) of diacetate II (methane type) obtained in step 1 was added, and the mixture was stirred at room temperature for 3 hours. After completion of the reaction, 10 mL of acetonitrile and 10 mL of diethyl ether were added to the resulting reaction solution and stirred for 10 minutes, followed by filtration to obtain crude crystals. The obtained crude crystals were washed with 20 mL of diethyl ether and then dried to obtain 358 mg of the desired product as pale yellow crystals (91%).
Physical property data:
mp 123-125 ° C
¹ H-NMR (CDCl ₃ / CF ₃ CO ₂ H (= 10/1), 300 MHz): δ8.20 (d, J = 8.7 Hz, 8H), 7.70 (d, J = 8.1 Hz, 8H), 7.41 (d, J = 8.7Hz, 8H), 7.30 (d, J = 8.1Hz, 8H), 2.43 (s, 12H), 2.26 (s, 12H).
IR (KBr): 3645 w, 3624 w, 3583 w, 2353 w, 1759 m, 1732 m, 1634 m, 1445 w, 1180 s, 1126 w, 1036 m, 1009 m, 912 w, 814 m, 702 m cm ^-1 .

Experimental Example 1 Oxidation of phenol to quinone monoacetal

* MeO = methoxy, MeOH = methanol
3,4,5-trimethoxyphenol 184.2 mg was dissolved in 5 mL of methanol, 354.1 mg of diacetate I (adamantane type) (compound 1) obtained in Example 1 was added, and the mixture was stirred at 20-30 ° C. for 10 minutes. It was. After confirming the disappearance of the raw material by TLC, 10 mL of methanol was added to the obtained reaction solution, filtered through a glass filter, and the residue was washed several times with methanol. The obtained filtrate was centrifuged, and the supernatant was concentrated to quantitatively obtain quinone monoacetal (2,4,4,5-tetramethoxy-2,5-cyclohexadienone) (yield: 100% ). Subsequently, the oxidation reagent diacetate I (adamantane type) was recovered as an iodine body (236.1 mg, recovery rate: 100%). The results are shown in Table 1.
Physical property data: ¹ H-NMR (CDCl ₃ ): δ5.57 (s, 2H), 3.74 (s, 6H), 3.21 (s, 6H)

Comparative Example 1
Except for using 1 equivalent of phenyliodine diacetate [PhI (OAc) ₂ : PIDA] instead of diacetate I used in Experimental Example 1, the same procedure as in Experimental Example 1 was performed to quantitatively determine quinone monoacetal. Obtained (yield: 91%). The results are shown in Table 1.
PIDA, which is the oxidizing reagent, becomes iodobenzene after use in the reaction, and is not suitable for recovery because it is a volatile liquid.

Comparative Example 2
[Poly (diacetoxyiodo) styrene: PDAIS] was used instead of the diacetate used in Experimental Example 1, and the same operation as in Experimental Example 1 was performed except that the number of reaction sites was 1 equivalent to the substrate. The quinone monoacetal was quantitatively obtained (yield: 91%). The results are shown in Table 1.
PDAIS, which is the oxidation reagent, had a recovery rate of almost 100%, but the yield during re-oxidation performed for reuse was low (yield: 60-80%), and polymer degradation also occurred. Since it progressed, the yield when re-using as an oxidizing reagent again was 50 to 80% in terms of recovered polyiodostyrene.

Experimental Example 2. Oxidation reaction of alcohols (1)

  After dissolving 31.8 μl of 2-octanol in 1 mL of water, 23.8 mg (1.0 eq) of KBr was added and stirred for 5 minutes, and the mixture was diacetate I (adamantane type) obtained in Example 1 (compound). 1) 77.9 mg (0.055 mmol, 1.1 × 1/4 eq) was added and the reaction was stirred at 20-30 ° C. for 1.5 hours. After completion of the reaction, the obtained reaction solution was poured into a filter [trade name: Varian BOND ELUT C2 or C8] to adsorb the target product. Next, the filter is washed with 20 mL of water to remove KBr, 20 mL of methanol is added, the adsorbed target product is discharged, and 2-octanone is quantitatively determined as a single organism by gas chromatography (GC) measurement. Obtained (yield: 100%). Subsequently, the oxidation reagent, diacetate I (adamantane type), was recovered as iodine (52.0 mg, yield: 100%). The results are shown in Table 2.

Comparative Example 3
2-octanone was quantitatively obtained in the same manner as in Experimental Example 1 except that 1 equivalent of iodosylbenzene [PhIO] was used instead of the diacetate used in Experimental Example 1. (Yield: 100% ). The results are shown in Table 2.
PhIO, which is the oxidizing reagent, becomes iodobenzene after use in the reaction, which is a volatile liquid and is not suitable for recovery.

Comparative Example 4
Instead of the diacetate used in Experimental Example 1, [poly (diacetoxyiodo) styrene: PDAIS] was used in such an amount that the number of reaction sites was 1 equivalent to the substrate, and the reaction time was 7 hours. The same operation as in Experimental Example 1 was performed to quantitatively obtain 2-octanone (yield: 100%). The results are shown in Table 2.
PDAIS, which is the oxidation reagent, had a recovery rate of almost 100%, but the yield during re-oxidation performed for reuse was low (yield: 60-80%), and polymer degradation also occurred. Since it progressed, the yield when re-using as an oxidizing reagent again was 50 to 80% in terms of recovered polyiodostyrene.

Experimental Example 3. Α-Tosyloxylation of ketones (1)

  After dissolving 133 μl (1 mmol) of propiophenone in 2.5 mL of anhydrous acetonitrile under a nitrogen atmosphere, 424.3 mg (0.25 mmol, 1 × 1/4 eq) of hydroxytosiloxy compound I (adamantane type) obtained in Example 2 was added. The mixture was added and stirred for 3 hours under reflux with heating. After completion of the reaction, 20 mL of methanol was added to the obtained reaction solution and filtered through a glass filter. The target product was extracted twice with 10 mL of methanol, and the filtrate was concentrated and subjected to liquid column chromatography [hexane / ethyl acetate = 4. / 1] gave 231.4 mg of the desired tosyloxy form (1-phenyl-2-tosyloxypropanone) (yield: 76%). Moreover, the hydroxytosiloxy body (adamantane type) which is the said oxidation reagent was collect | recovered as an iodine body (230.3 mg, recovery rate: 98%). The results are shown in Table 3.

Comparative Examples 5-7.
The same operation as in Experimental Example 3 was performed except that the following iodine reagent was used instead of the hydroxytosyloxy compound of the present invention used in Experimental Example 3. Table 3 shows the recovery rate of each recovered iodine reagent after the completion of the reaction.

* [PS] = poly [4-hydroxy (tosyloxy) iodo] styrene
[PMS] = poly {α-methyl [4-hydroxy (tosyloxy) iodo] stylene}
The oxidation reagent PhI (OH) OTs used in Comparative Example 5 becomes iodobenzene after use in the reaction, which is a volatile liquid and is not suitable for recovery. Further, the oxidizing reagents PS and PMS used in Comparative Examples 6 and 7 have a recovery rate of 100%, but the yield at the time of reoxidation performed for reuse is low (yield: 60-80%), Moreover, since the deterioration of the polymer also proceeds, the yield when reused again as an oxidizing reagent was 50 to 80% in terms of the recovered polyiodostyrene.

Experimental Example 4 Oxidative biaryl coupling reaction of phenyl ethers (1)

Under a nitrogen atmosphere, BF ₃ -Et ₂ O 139.4 μl (1.1 mmol) was added to a solution of 4-bromoveratrole 143.9 μl (1 mmol) in 5 mL of anhydrous dichloromethane at −40 ° C. 254.2 mg (0.138 mmol) of the bistrifluoroacetate I obtained in step 1 (adamantane type) was added, and the mixture was stirred at -78 to -48 ° C for 3 hours. After completion of the reaction, 10 mL of saturated aqueous sodium bicarbonate and 10 mL of saturated aqueous sodium thiosulfate solution were added to the resulting reaction solution at 0 ° C. and stirred for 10 minutes. The resulting reaction solution was extracted twice with 15 mL of dichloromethane, washed with saturated brine, dried over sodium sulfate (sodium sulfate), and concentrated. Then, 20 mL of methanol was added to the resulting residue, and the precipitate was filtered with a glass filter. It was filtered and the filtrate was concentrated and centrifuged. The operation of taking the supernatant and adding methanol again to the resulting residue was repeated several times. The combined supernatant was concentrated and the target product was obtained by liquid column chromatography (yield: 98%). The oxidization reagent, bistrifluoroacetate (adamantane type), was recovered as iodine (130.3 mg, yield: 100%).

Experimental Example 5. Oxidation reaction of phenols to quinones.

  Diacetate II (methane type) obtained in Example 4 (compound 4) was obtained by dissolving 92.1 mg (0.5 mmol) of 3,4,5-trimethoxyphenol in 2.5 mL of acetonitrile-water (= 4/1) mixed solvent. 162.0 mg (0.125 mmol) was added, and the mixture was stirred at room temperature for 15 minutes. After confirming the disappearance of the raw materials by TLC, the mixture was further stirred at room temperature for 15 minutes, 5 mL of the acetonitrile-water mixed solvent was added to the resulting reaction solution, filtered through a glass filter, and the residue was counted with the acetonitrile-water mixed solvent. Washed twice. The obtained filtrate was centrifuged, and the supernatant was concentrated to obtain quinone (2,6-dimethoxy-1,4-benzoquinone) quantitatively (yield: 96%). Next, diacetate II (methane type), which is the oxidizing reagent, was recovered almost quantitatively as an iodine body (101.9 mg, recovery rate: 99%). Further, the yield when the diacetate II was reused as an oxidizing reagent was approximately 90 to 93% from the recovered iodine. These results are shown in Table 4.

Comparative Examples 8 and 9
An oxidation reaction similar to that in Experimental Example 5 was performed using PIDA (1.1 eq.) (Comparative Example 8) and PDAIS (1.1 eq.) (Comparative Example 9) instead of the diacetate II used in Experimental Example 5. In any case, quinone was quantitatively obtained. However, when PIDA was used, the reaction was completed at the same level as in Experimental Example 5, but PIDA could not be recovered. In addition, when PIDAS was used, the reaction was not completed in 30 minutes, and more time was required.
In addition, PIDA becomes iodobenzene after use in the reaction, which is a volatile liquid and is not suitable for recovery. PDAIS had a recovery rate of almost 100%, but the yield during re-oxidation performed for reuse is low (yield: 60-80%), and polymer degradation also proceeds. The yield when reused as an oxidizing reagent was 50 to 80% in terms of recovered polyiodostyrene. These results are shown together in Table 4.

Experimental Example 6. Oxidation reaction of alcohols (2)

  After dissolving 31.2 mg (0.2 mmol) of L-menthol in 1 mL of water, 12.0 mg (0.1 mmol, 0.5 eq.) Of KBr was added and stirred for several minutes, and the diacetate obtained in Example 4 was added to the mixture. Form II (methane type) (compound 4) 71.3 mg (0.055 mmol, 1 × 1/4 eq.) Was added, and the mixture was stirred at room temperature for 1.5 hours. After completion of the reaction, the resulting reaction solution was treated in the same manner as in Experimental Example 2 to quantitatively obtain the desired product (yield: 100%). Subsequently, the oxidation reagent diacetate II was quantitatively recovered as iodine (44.9 mg, yield: 99%). Further, the yield when the diacetate II was reused as an oxidizing reagent was approximately 90 to 93% from the recovered iodine. These results are shown in Table 5.

Comparative Examples 10 and 11
An oxidation reaction similar to that in Experimental Example 6 was performed using PIDA (1.2 eq.) (Comparative Example 10) and PDAIS (1.2 eq.) (Comparative Example 11) instead of the diacetate II used in Experimental Example 6. However, each target product was quantitatively obtained in a yield of 91%.
However, PIDA becomes iodobenzene after use in the reaction, which is a volatile liquid and is not suitable for recovery. PDAIS, on the other hand, had a recovery rate of almost 100%, but the yield during re-oxidation performed for reuse is low (yield: 60-80%), and polymer degradation also proceeds. The yield when reused again as an oxidizing reagent was 50 to 80% in terms of recovered polyiodostyrene. These results are also shown in Table 5.

Experimental Example 7. Oxidative biaryl coupling reaction (2)
Under a nitrogen atmosphere, BF ₃ -Et ₂ O ( ₂ eq.) Was added at −40 ° C. to a solution of 4-bromoveratrole 43.4 mg (0.2 mmol) dissolved in 2.5 mL of anhydrous dichloromethane. 47.5 mg (0.0275 mmol) of the bistrifluoroacetate compound II (methane type) (compound 9) obtained in (1) above was added, and the mixture was stirred at -40 ° C. for 3 hours. After completion of the reaction (completed in about 1 hour), the reaction solution was concentrated, 20 mL of methanol was added to the resulting residue, the precipitate was collected by filtration with a glass filter, and the filtrate was concentrated and centrifuged. The operation of taking the supernatant and washing the residue with methanol was repeated several times. The washing liquid and the supernatant liquid were combined and concentrated, and 42.4 mg of the target biaryl coupling product was obtained by liquid column chromatography (yield: 98%). The oxidizing reagent, bistrifluoroacetate II (methane type), could be recovered as iodine (22.0 mg, yield: 97%).

Experimental Example 8. Α-Tosyloxylation of ketones (2)
In a nitrogen atmosphere, propiophenone 40.2 mg (0.3 mmol) was dissolved in anhydrous acetonitrile 1.5 mL, and then hydroxytosiloxy compound II (methane type) obtained in Example 10 (compound 10) 118.2 mg (0.075 mmol, 1 × 1/4 eq) was added, and the mixture was stirred at 70 ° C. for 3 hours. After completion of the reaction, the obtained reaction solution was filtered through a glass filter, and then the filtrate was concentrated and subjected to liquid column chromatography [hexane / ethyl acetate = 4/1] to obtain the desired tosyloxy compound (1-phenyl-2-tosyloxy). Propanone) 60.2 mg was obtained (yield: 66%). Moreover, the hydroxytosiloxy body II (methane type) which is the said oxidation reagent was recoverable as an iodine body (60.6 mg, recovery rate: 98%).

  As is clear from the results of Experimental Examples 1 to 8, the hypervalent iodine compound according to the present invention is useful as various oxidation reaction or tosiloxy reaction reagents.

  Moreover, as is clear from the results of Experimental Examples 1 to 3, Comparative Examples 1 to 7, and Tables 1 to 3, the hypervalent iodine reagent of the present invention exhibits high reactivity equal to or higher than that of the monomer reagent, It is clear that the recovery rate and reuse rate of iodine is almost 100%, and that it can be recovered and reused more easily than the monomer reagent and polymer reagent.

Experimental Examples 9-14. Selective α-tosiloxylation of ketones

Various iodine reagents shown in Table 6 are used as oxidizing reagents, various ketones (R ′ is described in Table 6 below) as substrates, and tosyl acid monohydrate (TsOH · H ₂ O) is 1 per substrate. Except for adding an equivalent amount, α-tosyloxylation reaction was carried out in the same manner as in Experimental Example 3 to obtain 3-tosyloxy isomer (a) and 1-tosyloxy isomer (b). However, in Experimental Example 10 using Compound 10 (methane type) which is a hydroxytosyloxy compound, the reaction was performed without adding TsOH · H ₂ O. These results are also shown in Table 6.

  As is clear from the results of Experimental Examples 9 to 14 and Comparative Examples 12 and 13, when the tosyloxylation reaction was performed using the hypervalent iodine compound according to the present invention as an oxidizing reagent, compared to the conventional iodine reagent, It can be seen that the α-position of the substrate is selectively tosylated, that is, the 3-tosyloxy form is produced with high selectivity.

  Further, as is clear from the results of Experimental Examples 9 and 11, among the hypervalent iodine compounds according to the present invention, the yield obtained by performing the tosiloxylation reaction using the methane type as an oxidizing reagent rather than the adamantane type was obtained. It can be seen that the 3-tosiloxy compound is highly selective.

Claims (14)

General formula [1]

{Wherein Z is a carbon atom or a formula [2]

And T represents an arylene group or divalent heterocyclic group which may have a substituent, q represents an integer of 1 to 5, and R ¹ represents: General formula [3]

[Wherein R ² and R ³ are each independently an allyl group, cyclopentadienyl group, hydroxyl group, azide group, cyano group, isocyanate group, thiocyanate group, phthalimide group, haloalkyl group, alkoxy group, substituted Aryl group which may have a group, arylthio group which may have a substituent, heterocyclic group, general formula [4]

(Wherein R ⁴ represents an alkyl group, a haloalkyl group, an aryl group optionally having a substituent, a heterocyclic group, a carboxyalkyl group or a carboxyaryl group), an acyloxy group represented by the general formula [5 ]

(Wherein R ⁵ represents an alkyl group, an aryl group which may have a substituent, a heterocyclic group or a camphor group), a general formula [6]

(In the formula, R ⁶ represents an alkyl group or an aryl group which may have a substituent, and R ⁷ represents an alkoxycarbonyl group, an aryloxycarbonyl group, an aralkyloxycarbonyl group, an alkylsulfonyl group or an arylsulfonyl group. A group represented by the general formula [7]

(Wherein R ⁸ and R ⁹ are each independently a hydrogen atom, a benzenesulfonyl group, a cyano group, an alkyl group, a haloalkyl group, an alkoxy group, an aryl group that may have a substituent, an aralkyl group, or a cyano group. An alkyl group, an alkyl group which may have an oxygen atom, or an acyloxy group (except when R ⁸ and R ⁹ are both hydrogen atoms)), an alkenyl group represented by the general formula [8]

(In the formula, R ¹⁰ represents an alkyl group, an aryl group which may have a substituent, an aralkyl group, a heterocyclic group, an alkyl group which may have an oxygen atom, an acyl group, an alkoxycarbonyl group, an aralkyloxy group. A carbonyl group, a trialkylsilyloxy group, an alkyldiphenylsilyloxy group, a triphenylsilyloxy group, a benzenesulfonyl group, an allyl group or a cyano group.) Or an alkynyl group represented by the general formula [9]

(Wherein R ¹¹ represents an amino-protected amino acid residue). A group represented by the general formula [10]

Wherein, R ¹² is an optionally substituted aryl group, a group represented by the heterocyclic group or the above-mentioned general formula [8], Y ₁ is a halide, BF 4 _- ^{(tetrafluoroborate)} , PF ₆ ^- (hexafluorophosphate), ClO ₄ ^- (perchlorate), HSO ₄ ^- (hydrogensulfate sulfate) or the general formula [11]

(Wherein R ¹³ represents an alkyl group, a haloalkyl group, an aryl group which may have a substituent, or a heterocyclic group) or a general formula [12]

(Wherein R ¹⁴ represents an alkyl group, a haloalkyl group, an aryl group which may have a substituent or a heterocyclic group) and an anion derived from a sulfonic acid. A group represented by the general formula [13]

[Wherein T ₁ represents an alkylene group, an arylene group, a 1,2-diacyloxyethylene group, or a general formula [14]

(Wherein R ¹⁵ represents an amino protecting group and m represents 1 or 2). A group represented by the general formula [15]

Wherein R ¹⁶ represents a lower alkyl group, a halo lower alkyl group or an aryl group which may have a substituent, and a general formula [16]

(Wherein R ¹⁷ and R ¹⁸ each independently represents a nitro group, a cyano group or a benzenesulfonyl group), an ylide group represented by the general formula [17]

(In the formula, Y ₂ represents a halide, tetrafluoroborate, hexafluorophosphate, perchlorate, hydrogen sulfate or a carboxylic acid represented by the general formula [11] or an anion derived from the sulfonic acid represented by the general formula [12]. N represents an integer of 1 to 5, and Z, T, and q are the same as above.) Or an iodosyl group. } The hypervalent iodine compound shown by these. The compound of claim 1, wherein Z is a carbon atom. The compound according to claim 1, wherein Z is a tetravalent adamantane residue represented by the formula [2]. The compound according to any one of claims 1 to 3, wherein T is a p-phenylene group and q is 1. The compound in any one of Claims 1-3 whose R < ¹ > is group shown by general formula [3]. The compound according to claim 5, wherein R ² and R ³ are both acetyloxy groups or trifluoroacetyloxy groups. The compound according to claim 5, wherein one of R ² and R ³ is a hydroxyl group and the other is a tosyl group. The compound in any one of Claims 1-3 whose R < ¹ > is group shown by general formula [10]. The compound according to claim 8, wherein R ¹² is a tolyl group. The compound according to claim 8, wherein Y ₁ is an anion derived from trifluoromethanesulfonic acid. The compound in any one of Claims 1-3 whose R < ¹ > is group shown by general formula [17]. Y ₂ is a tetrafluoroborate or hexafluorophosphate, compound of claim 11. The compound according to claim 11, wherein n is 1. The compound according to any one of claims 1 to 3, wherein R ¹ is an iodosyl group.