CN112121852B - Catalyst composition and use of catalyst composition or catalyst for catalyzing nucleophilic substitution reaction - Google Patents

Catalyst composition and use of catalyst composition or catalyst for catalyzing nucleophilic substitution reaction Download PDF

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CN112121852B
CN112121852B CN202010880701.4A CN202010880701A CN112121852B CN 112121852 B CN112121852 B CN 112121852B CN 202010880701 A CN202010880701 A CN 202010880701A CN 112121852 B CN112121852 B CN 112121852B
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李乐
梁大成
魏明杰
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Sun Yat Sen University
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Abstract

The present invention provides a catalyst composition comprising: (a) at least one catalyst, (b) at least one silicon additive, and (c) optionally a base. The invention also provides the use of a catalyst composition or catalyst according to the invention for the catalysis of SO-containing catalysts2Use of a compound of the F group for nucleophilic substitution reaction with a nucleophile. The catalyst or catalyst composition according to the present invention can sufficiently activate the-SO-containing2A compound of the F group and a nucleophile, thereby enabling them to efficiently undergo nucleophilic substitution reactions. In addition, the nucleophilic substitution reaction using the catalyst composition or the catalyst according to the present invention is simple to operate, has high yield, and is suitable for mass production.

Description

Catalyst composition and use of catalyst composition or catalyst for catalyzing nucleophilic substitution reaction
Technical Field
The invention relates to the field of organic synthesis, in particular to a catalyst composition and application of the catalyst composition or the catalyst to catalysis of nucleophilic substitution reaction.
Background
Sulfonyl fluoride plays a very important role in synthetic chemistry because of its stable chemical properties and good functional group compatibility, and is receiving increasing attention from chemists and pharmacologists. Compared with sulfonyl chloride, the reaction of sulfonyl fluoride and a nucleophilic reagent has the defects of low efficiency, narrow substrate range and the like. The development of a catalyst system for nucleophilic substitution reactions that activate sulfonyl fluorides is a major and difficult point in the research field of sulfonyl fluorides.
The methods for activating nucleophilic substitution reactions of sulfonyl fluorides reported in the literature are very limited. For example, CN 107266392 a describes a method for synthesizing aminosulfonate compounds directly in a solvent at room temperature without using an external base, using aryl fluorosulfonate and amine as substrates, but the method is limited to very active substrates and is not applicable to less active substrates. In addition, Sharpless et al (see the document Angew. chem. int. Ed.2014,53, 9430-9448) describe the reaction of fluorosulfonate esters with phenols as nucleophiles, using conventional catalysts DBU or BEMP, which have a high catalytic activity towards phenolic nucleophiles but a low catalytic activity towards other types of nucleophiles, such as amines.
Nicholas D.ball et al (see org.Lett.2018,20,3943-2)2Activation of SO-containing2F group-containing compounds, activated-SO2The compound of F group further reacts with nitrogen-containing nucleophilic reagent to synthesize-SO2Methods for NRR' compounds. This system requires the use of large amounts of expensive Ca (NTf)2)2The production cost is increased, the large-scale use of the method in synthesis is severely limited, and meanwhile, the inconvenience is brought to separation and purification; meanwhile, the method is lack of reports on substrates with larger steric hindrance.
As mentioned above, containing-SO2The activation of the compound of the F group presents the following problems: 1) there is no broad spectrum of mild methods; 2) the use of stoichiometric amounts of expensive metal salts such as Ca (NTf) is required2)2Not suitable for industrial scale use and not meeting the requirements of green chemistry; 3) in the presence of-SO2In the reaction of F group compounds with nucleophiles, the reactivity is heavily dependent on the presence of-SO2The self-chemistry of the compound of the F group and the nucleophile, the substrate range is limited. Therefore, it is required to develop a catalyst suitable for various types of-SO-containing compounds2Catalyst system of a compound of group F and a nucleophilic substitution reagent, which catalyst system is particularly suitable for-SO-containing catalysts which are difficult to react using conventional activation methods2A compound of group F.
Disclosure of Invention
To overcome these problems of the prior art, it is an aspect of the present invention to provide a catalyst composition comprising:
(a) at least one catalyst that is a compound of formula (I) or a compound of formula (II), or a combination thereof:
Figure BDA0002654021170000021
in the formulae (I) and (II), R1And R2Are each independently of the others selected from hydrogen, hydroxy, halogen, C1-C6Alkyl radical, NO2、C1-C6Alkoxy, amino, C1-C6Alkyl monosubstituted amino, C1-C6Alkyl-disubstituted amino, C1-C6Haloalkyl, C1-C6An alkyloxycarbonyl group; or R1And R2Together with the carbon atom to which they are attached form ring a;
the ring A is selected from: a monocyclic or compensated bicyclic aromatic ring having 6-10 carbon atoms; a monocyclic or compensated bicyclic heteroaryl ring having 5-10 ring atoms comprising 1-3 heteroatoms selected from N, O, S and any combination thereof; a monocyclic or fused bicyclic carbocycle having 3-10 carbon atoms; a monocyclic or compensated bicyclic heterocycle having 3-10 ring atoms comprising 1-3 heteroatoms selected from N, O, S and any combination thereof;
said ring A being optionally substituted by one or more than one substituent RaSubstituted, each substituent RaIdentical or different, independently of one another, from the group consisting of hydroxyl, halogen, C1-C18Alkyl radical, NO2、C1-C18Alkoxy, amino, C1-C6Alkyl monosubstituted amino, C1-C6Alkyl-disubstituted amino, C1-C6Haloalkyl, C1-C6Alkyl oxycarbonyl radical, C6-C10Aryl, benzyl;
R3are respectively selected from hydrogen, hydroxyl, sulfydryl, halogen and C1-C6Alkyl radical, NO2、C1-C6Alkoxy, amino, C1-C6Alkyl monosubstituted amino, C1-C6Alkyl-disubstituted amino, C1-C6Haloalkyl, C1-C18Alkyloxycarbonyl, oxytris (pyrrolidinyl) phosphonium hexafluorophosphate, oxytris (pyrrolidinyl) phosphonium tetrafluoroborate, oxytris (dimethylamino) phosphonium hexafluorophosphate, oxytris (dimethylamino) phosphonium tetrafluoroborate, oxydi (dimethylamino) carbonium hexafluorophosphate, oxydi (dimethylamino) carbonium tetrafluoroborate, oxydi (pyrrolidinyl) carbonium hexafluorophosphate, oxydi (pyrrolidinyl) carbonium tetrafluoroborate, -OSO2C1-C6Alkyl, -OSO2C1-C8Perfluoroalkyl group, -OSO2C6-C10An aryl group;
(b) at least one additive, wherein the additive is a silicon-containing compound selected from the group consisting of: unsubstituted or substituted trimethylsilyl, C1-C4Alkyl radical, C1-C4Haloalkyl, phenyl, C1-C4Alkoxy or any combination thereof mono-or poly-substituted silane;
unsubstituted or by C1-C4Alkyl radical, C1-C4Haloalkyl, phenyl, C1-C4Alkoxy or any combination thereof mono-or poly-substituted disiloxane;
a compound of formula (III)
Figure BDA0002654021170000031
Wherein the substituent Re、Rf、Rg、Rh、Ri、Rj、RkIdentical or different, independently of one another, from hydrogen, C1-C4Alkyl radical, C1-C4Haloalkyl, phenyl, C1-C4An alkoxy group;
a compound of formula (IV)
Figure BDA0002654021170000032
Wherein R isl、Rm、Rn、Ro、Rp、RqIdentical or different, independently of one another, from hydrogen, C1-C4Alkyl radical, C1-C4Halogenated alkyl, phenyl,C1-C4An alkoxy group;
a compound of formula (V)
Figure BDA0002654021170000033
Wherein R isr、Rs、Rt、Ru、Rv、Rw、Rx、RyIdentical or different, independently of one another, from hydrogen, C1-C4Alkyl radical, C1-C4Haloalkyl, phenyl, C1-C4Alkoxy, n is 1 to 2000, preferably 10 to 1000, more preferably 100-500; and
(c) optionally a base, wherein the base is an organic base or an inorganic base,
the organic base is selected from R11R12NR13Wherein R is11、R12And R13Independently of one another, from hydrogen, C1-C4An alkyl group; r21R22N-Y-NR23R24Y is C1-C3Alkylene radical, R21、R22、R23And R24Independently of one another, from hydrogen, C1-C4An alkyl group; unsubstituted or substituted by halogen, C1-C4Alkyl-substituted diaza or triazabicyclo C6-C12An olefin;
Figure BDA0002654021170000041
Figure BDA0002654021170000042
and
Figure BDA0002654021170000043
wherein R is41、R42、R43、R44、R45Independently of one another, from hydrogen, C1-C4An alkyl group;
the inorganic base is selected from carbonates, phosphates, hydrides and C of alkali metals or alkaline earth metals1-C18An alkyl oxide.
In one embodiment, in the compound of formula (I) or formula (II), R1And R2Are each independently of the other selected from hydrogen, C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Haloalkyl, C1-C6An alkyloxycarbonyl group; or R1And R2Together with the carbon atom to which they are attached form ring a;
the ring A is selected from: a monocyclic or compensated bicyclic aromatic ring having 6-10 carbon atoms; a monocyclic or compensated bicyclic heteroaryl ring having 5-10 ring atoms comprising 1-3 heteroatoms selected from N, O, S and any combination thereof;
said ring A being optionally substituted by one or more than one substituent RaSubstituted, each substituent RaIdentical or different, independently of one another, from the group consisting of hydroxyl, halogen, C1-C18Alkyl radical, NO2、C1-C18Alkoxy, amino, C1-C6Alkyl monosubstituted amino, C1-C6Alkyl-disubstituted amino, C1-C6Haloalkyl, C1-C6Alkyl oxycarbonyl radical, C6-C10Aryl, benzyl;
R3are respectively selected from hydrogen, hydroxyl, sulfydryl, halogen and C1-C6Alkyl radical, NO2、C1-C6Alkoxy, amino, C1-C6Alkyl monosubstituted amino, C1-C6Alkyl-disubstituted amino, C1-C6Haloalkyl, C1-C18Alkyloxycarbonyl, oxytris (pyrrolidinyl) phosphonium hexafluorophosphate, oxytris (pyrrolidinyl) phosphonium tetrafluoroborate, oxytris (dimethylamino) phosphonium hexafluorophosphate, oxytris (dimethylamino) phosphonium tetrafluoroborate, oxydi (dimethylamino) carbonium hexafluorophosphate, oxydi (dimethylamino) carbonium tetrafluoroborate, oxydi (pyrrolidinyl) carbonium hexafluorophosphate, oxydi (pyrrolidinyl) carbonium tetrafluoroborate, -OSO2C1-C6Alkyl, -OSO2C6-C10An aryl group;
preferably, in the compound represented by formula (I) or formula (II), R1And R2Are each independently of the other selected from hydrogen, C1-C6An alkyloxycarbonyl group; or R1And R2Together with the carbon atom to which they are attached form ring a;
the ring A is selected from: a benzene ring or a naphthalene ring; a monocyclic or compensated bicyclic heteroaryl ring having 5-10 ring atoms comprising 1 heteroatom selected from N, O, S;
said ring A being optionally substituted by one or more than one substituent RaSubstituted, each substituent RaIdentical or different, independently of one another, from the group consisting of hydroxyl, halogen, C1-C18Alkyl radical, NO2、C1-C18Alkoxy, amino, C1-C6Alkyl monosubstituted amino, C1-C6Alkyl-disubstituted amino, C1-C6Haloalkyl, C1-C6Alkyl oxycarbonyl radical, C6-C10Aryl, benzyl;
R3are respectively selected from hydrogen, hydroxyl, sulfydryl, halogen and C1-C6Alkyl radical, NO2、C1-C6Alkoxy, amino, C1-C6Alkyl monosubstituted amino, C1-C6Alkyl-disubstituted amino, C1-C6Haloalkyl, C1-C18Alkyloxycarbonyl, oxytris (pyrrolidinyl) phosphonium hexafluorophosphate, oxytris (pyrrolidinyl) phosphonium tetrafluoroborate, oxytris (dimethylamino) phosphonium hexafluorophosphate, oxytris (dimethylamino) phosphonium tetrafluoroborate, oxydi (dimethylamino) carbonium hexafluorophosphate, oxydi (dimethylamino) carbonium tetrafluoroborate, oxydi (pyrrolidinyl) carbonium hexafluorophosphate, oxydi (pyrrolidinyl) carbonium tetrafluoroborate, -OSO2C1-C6Alkyl, -OSO2C6-C10And (4) an aryl group.
In another embodiment, the additive is selected from the group consisting of C1-C3Alkyl radical, C1-C2Alkoxy or phenyl or any combination thereofA substituted or polysubstituted silane; quilt C1-C4Alkyl or phenyl or any combination thereof; a compound of formula (III) wherein the substituent Re、Rf、Rg、Rh、Ri、Rj、RkIdentical or different, independently of one another, from hydrogen, C1-C4An alkyl group; a compound of formula (IV) wherein Rl、Rm、Rn、Ro、Rp、RqIdentical or different, independently of one another, from hydrogen, C1-C4An alkyl group; a compound of formula (V) wherein Rr、Rs、Rt、Ru、Rv、Rw、Rx、RyIdentical or different, independently of one another, from hydrogen, C1-C4An alkyl group;
preferably, the additive is selected from any one of the following compounds or any combination thereof:
Figure BDA0002654021170000061
Figure BDA0002654021170000062
silicon dioxide, silica gel, C3H9OSi·(CH4OSi)n·C3H9Si, wherein n is 1-2000, preferably 10-1000, more preferably 100-500.
In one embodiment, the catalyst composition is for catalyzing the reaction of: containing-SO2F, with nucleophilic substitution by a nucleophile, in which case the catalyst: the molar ratio of the reactants is 1: 20000 to 1: 1, preferably 1: 2000 to 1: 1, more preferably 1: 200 to 1: 1; silicon-containing compound additive: the molar ratio of the reactants is 1: 20 to 20: 1, preferably 1: 10 to 10: 1, more preferably 1: 5 to 5: 1; when the nucleophile is an amine and is in excess relative to the reactants, the base (c) may be absent, when the nucleophile is not an amine or is not in excess relative to the reactants even if the nucleophile is an amine, the base (c) may be added,and a base (c): the molar amount of the catalyst is more than 0.2: 1.
In another embodiment, the organic base is selected from R11R12NR13Wherein R is11、R12And R13Independently of one another, from C1-C4An alkyl group; r21R22N-Y-NR23R24Y is ethylene, R21、R22、R23And R24Independently of one another, from hydrogen, C1-C4An alkyl group; unsubstituted diaza or triazabicyclo C6-C12An olefin;
Figure BDA0002654021170000071
Figure BDA0002654021170000072
and
Figure BDA0002654021170000073
wherein R is41、R42、R43、R44、R45Independently of one another, from C1-C4An alkyl group;
the inorganic base is selected from carbonates or phosphates of alkali metals;
preferably, the base is selected from triethylamine, diisopropyldiethylamine, 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD), 1, 4-diazabicyclo [2.2.2] octane (DABCO), potassium carbonate, cesium carbonate, potassium phosphate, 2-tert-butylimino-2-diethylamino-1, 3-dimethylperhydro-1, 3, 2-diazaphosphorus (BEMP) and 2-tert-butyl-1, 1,3, 3-tetramethylguanidine (Barton base);
preferably, the base is triethylamine or diisopropylethylamine.
Another aspect of the invention relates to the use of the foregoing catalyst composition or the foregoing catalyst for catalyzing an-SO-containing catalyst as shown below2The use of a compound of the F group for nucleophilic substitution reaction with a nucleophile,
Figure BDA0002654021170000074
for the catalyst or catalyst composition according to the invention, the reactant capable of catalyzing the nucleophilic substitution reaction comprises-SO2The type of the compound of the F group and the nucleophilic agent is not particularly limited. In principle, the catalyst or catalyst composition according to the invention is capable of activating the known various types of-SO-containing catalysts2Nucleophilic substitution reaction of a compound of the F group with a nucleophile. The catalyst or catalyst composition according to the invention is very active especially against amine nucleophiles. containing-SO in the absence of catalyst or in the presence of only catalyst suitable for other types of nucleophiles, e.g. phenols2Nucleophilic substitution reactions of the compounds of the F group with nucleophiles, in particular amines, cannot be carried out or are less reactive. In contrast, in the presence of a catalyst or catalyst composition according to the invention, containing-SO2The activity of nucleophilic substitution reaction of the compound of F group and nucleophilic reagent, especially amine, is obviously improved.
In the use of catalysts for catalysing SO-containing compounds2In the case of nucleophilic substitution reaction of the F group-containing compound, the amount of-SO is 1 equivalent to that of the compound2The amount of said catalyst is at least 0.0001 equivalent, preferably 0.2 equivalent. As for the amount of the base, when the nucleophile is an alkaline agent and contains-SO in an amount of 1 equivalent2Compound of group F when the nucleophile is 1.5 equivalents or more, no additional base may be added; in the case of non-basic reagents or in the case of 1 equivalent of-SO-containing reagent2When the amount of the basic nucleophile of the F group-containing compound added is 1.5 equivalents or less (for example, 1.2 equivalents), it is necessary to add an additional base in an amount corresponding to 1 equivalent of-SO-containing compound2The compound of the F group is at least 2 equivalents.
In the use of catalyst compositions for the catalysis of SO-containing catalysts2In the case of nucleophilic substitution reaction of the compound of group F, the catalyst is used in an amount of at least 0.0001 equivalent relative to 1 equivalent of the sulfonyl fluoride compoundPreferably 0.2 equivalents; the silicon additive is used in an amount of at least 0.5 equivalents, preferably 2 equivalents. As for the amount of the base, when the nucleophile is an alkaline agent and contains-SO in an amount of 1 equivalent2Compound of group F when the nucleophile is 1.5 equivalents or more, no additional base may be added; in the case of non-basic reagents or in the case of 1 equivalent of-SO-containing reagent2When the amount of the basic nucleophile of the F group-containing compound added is 1.5 equivalents or less (for example, 1.2 equivalents), it is necessary to add an additional base in an amount corresponding to 1 equivalent of-SO-containing compound2The compound of the F group is at least 2 equivalents.
In the present invention, it contains-SO2Compounds of the F group include, but are not limited to SO2F2Sulfonyl fluoride compounds, fluorosulfonate esters, fluorosulfonamide compounds; nucleophiles include, but are not limited to, phenolic compounds, amine compounds, salts of fluorine and its isotopes, alcohol compounds, thiol compounds, and thiophenol compounds.
The solvent used in the nucleophilic substitution reaction is an organic solvent or a solvent-free solvent, and the kind and amount of the organic solvent are not particularly limited as long as the reactants and the catalyst or the catalyst composition can be partially dissolved. In one embodiment, the solvent is selected from C1-C4Alcohol solvent, C1-C4Nitrile solvent, C1-C4Halogenated hydrocarbon solvent, C6-C10Aromatic hydrocarbon solvent, C2-C4Sulfone solvent and C3-C6An amide solvent; preferably, the solvent is selected from methanol, ethanol, isopropanol, tert-butanol, acetonitrile, dichloromethane, toluene, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide; more preferably, the solvent is dichloromethane, N-methylpyrrolidone, dimethylsulfoxide or N, N-dimethylformamide. In one embodiment, the solvent is used in an amount of 1 to 10mL, preferably 1 to 5mL, relative to 1mmol of the sulfonyl fluoride compound.
In one embodiment, the-SO is contained with respect to 1 equivalent2Compounds of the F group, said nucleophilesThe amount of reagent used is 1 to 10 equivalents, preferably 1 to 5 equivalents, more preferably 1 to 4 equivalents, and even more preferably 1 to 2 equivalents.
According to the invention, different-SO-containing substances are targeted2The nucleophilic substitution reaction of the compound of the F group with a different nucleophile is carried out for a different time, and there is no particular limitation as long as the reaction can be completed. For example, the reaction time may be at least 1 hour, at least 2 hours, 3 to 10 hours, or 3 to 7 hours.
According to the invention, different-SO-containing substances are targeted2The nucleophilic substitution reaction of the compound of the F group with a different nucleophile is carried out at a different temperature, and is not particularly limited as long as the reaction can be completed. For example, the reaction temperature may be 20 to 100 ℃, 30 to 80 ℃, 30 to 50 ℃ or 30 to 40 ℃.
By using the catalyst or catalyst composition of the present invention, SO-containing compounds that are difficult to react by conventional activation methods2The nucleophilic substitution reaction of the compound of the F group with a nucleophile can proceed smoothly and the reaction yield is very high. In addition, containing-SO2The nucleophilic substitution reaction of the compound of the F group and the nucleophilic reagent can be carried out at a lower temperature, so that energy can be saved, environmental pollution can be reduced, and the requirement of green chemistry can be met.
By activation using the catalyst or catalyst composition of the invention, various-SO-containing catalysts2Compounds of the F group (RSO)2F) Can generate nucleophilic substitution reaction with nucleophilic reagent (NuH or NuM, wherein M is metal ion) to generate RSO2Nu。
Without being bound by any theory, the inventors have found that, although the reaction conditions of the present invention are mild, under the conditions of the specific catalyst system of the present invention, the-SO is contained2The compound of F group is fully activated, and the reactivity is very high. Therefore, compared with the method introduced in the prior literature, the catalyst system has the advantages of wide substrate range, higher reaction activity, mild reaction conditions, simple operation, no need of using expensive special reagents, suitability for large-scale production and capability of containing-SO2The use of compounds of the F group in synthesis provides a reliable technique.
Detailed Description
The abbreviations used in the present invention are summarized in the following table:
TABLE 1
Figure BDA0002654021170000101
Figure BDA0002654021170000111
Definition of
The term "C" as used in the present invention1-18Alkyl "refers to straight or branched chain alkyl groups containing 1 to 18 carbon atoms and includes, but is not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, tert-pentyl, hexyl, heptyl, octyl, nonyl, decane, and the like. In the present invention, C is preferable1-6Alkyl, more preferably C1-4An alkyl group.
The term "alkenyl" as used herein includes, but is not limited to, ethenyl, propenyl, butenyl, and the like.
The term "alkynyl" as used in the present invention includes, but is not limited to, ethynyl, propynyl, butynyl, and the like.
The term "C" as used in the present invention1-18Alkoxy "refers to straight or branched chain alkoxy groups containing 1 to 18 carbon atoms and includes, but is not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, t-butoxy, n-pentoxy, isopentoxy, tert-pentoxy, hexoxy, and the like. In the present invention, the alkoxy group is preferably C1-6Alkoxy, more preferably C1-4An alkoxy group.
The term "aromatic ring" as used in the present invention includes, but is not limited to, C6-C10For example, benzene ring, naphthalene ring.
The term "heteroaromatic ring" as used herein refers to a five to ten membered aromatic ring containing heteroatoms in the ring. The heteroatom may be N, O and/or an S heteroatom. The number of heteroatoms may be 1-3. In the present invention, the heteroaromatic ring includes, but is not limited to, furan, thiophene, pyrrole, thiazole, pyrazole, imidazole, pyridine, pyridazine, pyrimidine, pyrazine, pyran, oxazole, triazole.
The term "carbocycle" as used herein is a saturated or unsaturated cyclic group containing from three to ten carbon atoms. Carbocycles according to the present invention include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclobutadienyl, cyclopentadienyl, cyclohexadienyl.
The term "heterocycle" as used in the present invention is a saturated or unsaturated cyclic group containing a heteroatom in the ring and having three to ten atoms in the ring. The heteroatom may be N, O and/or an S heteroatom. The number of heteroatoms may be 1-3. In the present invention, the heterocyclic ring includes, but is not limited to, ethylene oxide, propylene oxide, dioxane, tetrahydrofuran, piperidine, and piperidine.
The term "halogen" as used herein includes, but is not limited to, fluorine, chlorine, bromine, iodine.
The alkali metal used in the present invention includes, but is not limited to, lithium, sodium, potassium, rubidium, and cesium, preferably sodium, potassium, and cesium, and more preferably potassium and cesium.
Alkaline earth metals useful in the present invention include, but are not limited to, magnesium, calcium.
In the present invention, a numerical range covers any number within the range.
In the present invention, the term "catalyst" has the same meaning as the term "activator" (activator), and may be used interchangeably.
The reagents used in the present invention are commercially available, for example, solvents, catalysts, additives, bases, SO-containing reagents used in the examples2Compounds and nucleophiles of the F group are commercially available from Sigma, Jiangsu Aikang, Annaiji, and the like.
The present invention will be further explained with reference to examples, but the present invention is not limited to these specific examples, and may be arbitrarily changed without departing from the spirit and scope of the invention.
Example 1
Figure BDA0002654021170000131
To the reaction flask was added 3-methyl-6- (diphenylphosphino) benzenesulfonyl fluoride (0.2mmol, 1.0eq), DMSO (250. mu.L), tert-butylamine (63.0. mu.L, 3.0eq), HOBt (27.0mg, 1.0 eq). The reaction mixture was heated to 40 ℃ and stirred for 24 hours. After the reaction was stopped. The yield calculated by nuclear magnetic phosphorus spectrum is 87%.
Example 2
The reaction was carried out in the same manner as in example 1 except that the catalyst HOBt was replaced with PyBOP, and the nuclear magnetic phosphorus spectrum calculation yield was 93%.
Example 3
The reaction was carried out in the same manner as in example 1 except that the catalyst HOBt was replaced with HOCT, and the nuclear magnetic phosphorus spectrum calculation yield was 75%.
Example 4
This example is a comparative example outside the scope of the invention. The reaction was carried out in the same manner as in example 1 except that HOBt was not added, and as a result, it was found that the reaction could not be carried out and the desired product could not be obtained.
Example 5
Figure BDA0002654021170000141
To the reaction flask were added p-toluenesulfonyl fluoride (41.8mg, 0.24mmol, 1.2eq), HOBt (5.4mg, 0.2eq), tert-butylamine (21.0. mu.L, 1.0eq), DMSO (250. mu.L), DIPEA (70.0. mu.L, 2.0eq), and trimethylethoxysilane (125.0. mu.L, 4.0eq), and reacted at 40 ℃ for 24 hours. The yield was 100% by nuclear magnetic calculation.
Example 6
The reaction was carried out in the same manner as in example 5 except that 4.0eq of trimethylethoxysilane as a catalyst was replaced with 2.0eq of hexamethylcyclotrisiloxane, and the nuclear magnetic calculation yield was 100%.
Example 7
The reaction was carried out in the same manner as in example 5 except that the catalyst trimethylethoxysilane was replaced with phenylsilane, and the nuclear magnetic calculation yield was 77%.
Example 8
The reaction was carried out in the same manner as in example 5 except that the catalyst trimethylethoxysilane was replaced with phenylsilane, and the amount of HOBt was increased to 1.0eq, and the nuclear magnetic calculation yield was 100%.
Example 9
The reaction was carried out in the same manner as in example 5 except that 4.0eq of trimethylethoxysilane as a catalyst was replaced with 2.0eq of tetraethyltitanate, and the nuclear magnetic calculation yield was 100%.
Example 10
The reaction was carried out in the same manner as in example 5 except that 4.0eq of trimethylethoxysilane as a catalyst was replaced with 2.0eq of hexamethyldisilazane, and the nuclear magnetic calculation yield was 100%.
Example 11
The reaction was carried out in the same manner as in example 5 except that 4.0eq of trimethylethoxysilane as a catalyst was replaced with 2.0eq of tetraethyl silicate, and the nuclear magnetic calculation yield was 100%.
Example 12
The reaction was carried out in the same manner as in example 5 except that the catalyst trimethylethoxysilane was replaced with silica gel (48.0mg, 4.0eq), and the nuclear magnetic calculation yield was 81%.
Example 13
Figure BDA0002654021170000151
To the reaction flask were added p-toluenesulfonyl fluoride (41.8mg, 0.24mmol, 1.2eq), HOBt (5.4mg, 0.2eq), tert-butylamine (21.0. mu.L, 1.0eq), DMSO (250. mu.L), DBU (1.0eq), 1,1,3, 3-tetramethyldisiloxane (71.0. mu.L, 2.0eq), and reacted at 25 ℃ for 24 hours. The yield by nuclear magnetic calculation was 94%.
Example 14
Figure BDA0002654021170000152
To the reaction flask were added p-toluenesulfonyl fluoride (41.8mg, 0.24mmol, 1.2eq), HOBt (5.4mg, 0.2eq), tert-butylamine (21.0. mu.L, 1.0eq), DMSO (250. mu.L), DABCO (2.0eq), 1,1,3, 3-tetramethyldisiloxane (71.0. mu.L, 2.0eq), and reacted at 40 ℃ for 24 hours. The nuclear magnetic calculation yield is 95%.
Example 15
Figure BDA0002654021170000153
To the reaction flask were added p-toluenesulfonyl fluoride (41.8mg, 0.24mmol, 1.2eq), HOBt (5.4mg, 0.2eq), tert-butylamine (21.0. mu.L, 1.0eq), DMSO (250. mu.L), potassium phosphate (2.0eq), 1,1,3, 3-tetramethyldisiloxane (71.0. mu.L, 2.0eq), and reacted at 40 ℃ for 24 hours. The yield was 100% by nuclear magnetic calculation.
Example 16
Figure BDA0002654021170000161
Add p-methoxyphenoxysulfonyl fluoride (41.2mg, 0.2mmol, 1.0eq), HOBt (5.4mg, 0.2eq), DMSO (250. mu.L), sodium carbonate (0.6eq), tert-butylamine (42.0. mu.L, 2.0eq), (TMS) to the reaction flask2O (85.0. mu.L, 2.0eq) was reacted at 35 ℃ for 10 hours. The yield by nuclear magnetic calculation was 79%.
Example 17
Figure BDA0002654021170000162
To the reaction flask were added p-toluenesulfonyl fluoride (41.8mg, 0.24mmol, 1.2eq), HOAt (5.4mg, 0.2eq), tert-butylamine (21.0. mu.L, 1.0eq), DMSO (250. mu.L), DIPEA (70.0. mu.L, 2.0eq), 1,1,3, 3-tetramethyldisiloxane (71.0. mu.L, 2.0eq), and reacted at 40 ℃ for 24 hours. The yield was 100% by nuclear magnetic calculation.
Example 18
The reaction was carried out in the same manner as in example 17 except that the catalyst HOAt was replaced with PyBOP, and the nuclear magnetic calculation yield was 100%.
Example 19
The reaction was carried out in the same manner as in example 17 except that the catalyst HOAt was replaced with HBTU, and the nuclear magnetic calculation yield was 90%.
Example 20
The reaction was carried out in the same manner as in example 17 except that the catalyst HOAt was replaced with TBTU, and the nuclear magnetic calculation yield was 88%.
Example 21
The reaction was carried out in the same manner as in example 17 except that the catalyst HOAt was replaced with HOCT, and the nuclear magnetic calculation yield was 100%.
Example 22
Except that the catalyst HOAt is replaced by CF3The reaction was carried out in the same manner as in example 17 except for-HOBt, and the nuclear magnetic calculation yield was 100%.
Example 23
The reaction was carried out in the same manner as in example 17 except that the catalyst HOAt was replaced with HOOBt, and the nuclear magnetic calculation yield was 73%.
Example 24
Figure BDA0002654021170000171
Add sulfonyl fluoride (273.8mg, 1.2mmol, 1.2eq), HOBt (1.4mg, 0.01eq), DMSO (1.25mL), DIPEA (350. mu.L, 2.0eq), and diphenylethylenediamine (212.5mg, 1.0eq), (TMS) to the reaction flask2O (425. mu.L, 2.0eq) was reacted at 60 ℃ for 37 hours. After the reaction, 70mL of dichloromethane and 15mL of water are added for washing for three times, and the mixture is dried, concentrated and subjected to column chromatography to obtain the product with the separation yield of 93%.
Example 25
Figure BDA0002654021170000172
To the reaction flask was added p-tert-butylbenzenesulfonyl fluoride (259.5mg, 1.2mmol, 1.2eq), HOBt (1.4mg, 0.01eq), DMSO (1.25mL), DIPEA (350. mu.L, 2.0eq), and 2-aminomethylpyridine (108.1mg, 1.0eq), (TMS)2O (425. mu.L, 2.0eq) was reacted at 60 ℃ for 24 hours. After the reaction, 70mL of ethyl acetate was added, followed by washing with 15mL of water three times, drying, concentrating, and performing column chromatography. The isolation yield was 90%.
Example 26
Figure BDA0002654021170000181
Add p-nitrobenzenesulfonyl fluoride (49.3mg, 0.24mmol, 1.2eq), HOBt (1.4mg, 0.05eq), DMSO (250 μ L), DIPEA (70.0 μ L, 2.0eq), p-methylaniline (21.4mg, 1.0eq), (TMS) to the reaction flask2O (64.0. mu.L, 2.0eq) was reacted at 28 ℃ for 24 hours. The nuclear magnetic calculation yield is 83%.
Example 27
Except that silicon additive (TMS)2The reaction was carried out in the same manner as in example 26 except that O was replaced with triethylsilane, and the nuclear magnetic calculation yield was 90%.
Example 28
Except that silicon additive (TMS)2The reaction was carried out in the same manner as in example 26 except that O was replaced with methyldiethoxysilane, and the nuclear magnetic calculation yield was 92%.
Example 29
Except that silicon additive (TMS)2The reaction was carried out in the same manner as in example 26 except that O was replaced with 1,1,3, 3-tetramethyldisiloxane, and the nuclear magnetic computation yield was 93%.
Example 30
Figure BDA0002654021170000182
To the reaction flask were added p-nitrobenzenesulfonyl fluoride (49.3mg, 0.24mmol, 1.2eq), HOBt-Cl (1.7mg, 0.05eq), DMSO (250. mu.L), DIPEA (70.0. mu.L, 2.0eq), aniline (18.6mg, 1.0eq), 1,1,3, 3-tetramethyldisiloxane (71.0. mu.L, 2.0eq), and the reaction was carried out at 25 ℃ for 24 hours. The nuclear magnetic calculation yield is 96%.
Example 31
Figure BDA0002654021170000191
3-pyridine sulfonyl fluoride (38.7mg, 0.24mmol, 1.2eq), HOBt (1.4mg, 0.05eq), DMSO (250. mu.L), DIPEA (70.0. mu.L, 2.0eq), and aniline (18.2. mu.L, 1.0eq), 1,1,3, 3-tetramethyldisiloxane (71.0. mu.L, 2.0eq) were added to the reaction flask and reacted at 25 ℃ for 24 hours. The nuclear magnetic calculation yield was 93%.
Example 32
Figure BDA0002654021170000192
To the reaction flask were added phosphinosulfonyl fluoride (86.0mg, 0.24mmol, 1.2eq), HOBt (20.0. mu.L, 0.01eq, 0.1M in DMSO), tert-butylamine (21.0. mu.L, 1.0eq), DMSO (230. mu.L), DIPEA (70.0. mu.L, 2.0eq), 1,1,3, 3-tetramethyldisiloxane (71.0. mu.L, 2.0eq), and reacted at 25 ℃ for 24 hours. The calculated yield of the nuclear magnetic phosphorus spectrum is 100 percent.
Example 33
The reaction was carried out in the same manner as in example 32 except that the silicon-containing additive 1,1,3, 3-tetramethyldisiloxane was replaced with hexamethyldisilazane, and the nuclear magnetic phosphorus spectrum calculation yield was 84%.
Example 34
The reaction was carried out in the same manner as in example 32 except that the silicon-containing additive 1,1,3, 3-tetramethyldisiloxane was replaced with methyldiethoxysilane, and the nuclear magnetic phosphorus spectrum calculation yield was 91%.
Example 35
The reaction was carried out in the same manner as in example 32 except that the silicon-containing additive 1,1,3, 3-tetramethyldisiloxane was replaced with polymethylhydrosiloxane (89.0mg, available from carbofuran, number average relative molecular mass: 1700-3200), and the nuclear magnetic phosphorus spectrum-calculated yield was 80%.
Example 36
This example is a comparative example outside the scope of the invention. The reaction was carried out in the same manner as in example 32 except that no silicon reagent was added, and as a result, it was found that the reaction did not proceed smoothly and the nuclear magnetic calculation yield was only 3%.
Example 37
Figure BDA0002654021170000201
To the reaction flask were added phosphine sulfonyl fluoride (71.6mg, 0.2mmol, 1.0eq), HOBt (20.0. mu.L, 0.01eq, 0.1M in DMSO), tert-butylamine (32.0. mu.L, 1.5eq), DMSO (230. mu.L), N, O-bis (trimethylsilyl) acetamide (44.5mg, 1.0eq), and reacted at 25 ℃ for 24 hours. The yield is 74% by calculation of nuclear magnetic phosphorus spectrum.
Example 38
The reaction was carried out in the same manner as in example 37 except that N, O-bis (trimethylsilyl) trifluoroacetamide, a silicon-containing additive, was replaced with N, O-bis (trimethylsilyl) trifluoroacetamide, and the nuclear magnetic phosphorus spectrum calculation yield was 85%.
Example 39
Figure BDA0002654021170000202
3-methyl-6- (diphenylphosphine) benzenesulfonyl fluoride (0.2mmol, 1.0eq), DMSO (250. mu.L), tert-butylamine (63.0. mu.L, 3.0eq), HOBt (27.0mg, 1.0eq), BSA (97.8. mu.L, 2.0eq) were added to the reaction flask. The reaction mixture was heated to 40 ℃ and stirred for 24 hours. The yield calculated by nuclear magnetic phosphorus spectrum is 92%.
Example 40
The reaction was carried out in the same manner as in example 39 except that the silicon-containing additive BSA was replaced with polymethylhydrosiloxane (89.0mg, available from carbofuran, number average relative molecular mass: 1700-.
EXAMPLE 41
The reaction was carried out in the same manner as in example 39 except that the silicon-containing additive BSA was replaced with tetraethyl silicate, and the nuclear magnetic phosphorus spectrum-calculated yield was 94%.
Example 42
The reaction was carried out in the same manner as in example 39 except that the silicon-containing additive BSA was replaced with silica gel, and the nuclear magnetic phosphorus spectrum was calculated to give a yield of 94%.
Example 43
The reaction was carried out in the same manner as in example 39 except that the silicon-containing additive BSA was replaced with diphenylsilane, and the nuclear magnetic phosphorus spectrum-calculated yield was 87%.
Example 44
Figure BDA0002654021170000211
To the reaction flask were added p-carboxybenzenesulfonyl fluoride (49.0mg, 0.24mmol, 1.2eq), HOBt (20.0. mu.L, 0.01eq, 0.1M in DMSO), di-n-propylamine (27.4. mu.L, 1.0eq), DMSO (230. mu.L), DIPEA (70.0. mu.L, 2.0eq), 1,1,3, 3-tetramethyldisiloxane (71.0. mu.L, 2.0eq), and the reaction was carried out at 25 ℃ for 24 hours. The nuclear magnetic calculation yield is 97%.
Example 45
Figure BDA0002654021170000221
To the reaction flask were added benzenesulfonyl fluoride (38.4mg, 0.24mmol, 1.2eq), 0.001M HOBt in DMSO (20.0. mu.L, 0.0001eq), tert-butylamine (21.0. mu.L, 1.0eq), DMSO (230. mu.L), DIPEA (70.0. mu.L, 2.0eq), 1,1,3, 3-tetramethyldisiloxane (71.0. mu.L, 2.0eq), and reacted at 60 ℃ for 24 hours. The yield was 100% by nuclear magnetic calculation.
Example 46
Figure BDA0002654021170000222
To the reaction flask were added benzenesulfonyl fluoride (32.0mg, 0.2mmol, 1.0eq), 0.0001M HOBt in DMSO (40.0. mu.L, 0.0002eq), 1-adamantanamine (60.5mg, 2.0eq), DMSO (210. mu.L), 1,1,3, 3-tetramethyldisiloxane (71.0. mu.L, 2.0eq), and reacted at 60 ℃ for 24 hours. The nuclear magnetic calculation yield is 99%.
Example 47
Figure BDA0002654021170000223
2,4, 6-Trimethylbenzenesulfonyl fluoride (242.7mg, 1.2mmol, 1.2eq), HOBt (1.4mg, 0.01eq), DMSO (1.25mL), tert-butylamine (105. mu.L, 1.0eq), DIPEA (350. mu.L, 2.0eq), 1,1,3, 3-tetramethyldisiloxane (355. mu.L, 2.0eq) were added to the reaction flask, and the reaction was carried out at 25 ℃ for 24 hours. After the reaction, 70mL of ethyl acetate was added, followed by washing with 15mL of water, 15mL of 1M hydrochloric acid, and 15mL of saturated saline, followed by drying, concentration, and column chromatography, and the isolation yield was 98%.
Example 48
Figure BDA0002654021170000231
To the reaction flask were added p-toluenesulfonyl fluoride (209.0mg, 1.2mmol, 1.2eq), HOBt (1.4mg, 0.01eq), DMSO (1.25mL), 1-adamantanamine (151.3mg, 1.0eq), DIPEA (350. mu.L, 2.0eq), 1,1,3, 3-tetramethyldisiloxane (355. mu.L, 2.0eq), and reacted at 25 ℃ for 24 hours. After the reaction, 70mL of ethyl acetate, 15mL of water, 15mL of 1M hydrochloric acid and 15mL of saturated saline are added for washing, drying, concentration and column chromatography are carried out, and the separation yield is 98%.
Example 49
Figure BDA0002654021170000232
P-fluorobenzenesulfonyl fluoride (214.0mg, 1mmol, 1.2eq), HOBt (1.4mg, 0.01eq), 3-amino-adamantanol (167.2mg, 1.0eq), DMSO (1.25mL), DIPEA (350. mu.L, 2.0eq), 1,1,3, 3-tetramethyldisiloxane (355. mu.L, 2.0eq) were added to the reaction flask, and the reaction was carried out at 25 ℃ for 24 hours. After the reaction, 70mL of ethyl acetate was washed with 15mL of water, 15mL of 1M hydrochloric acid, and 15mL of saturated saline, and the reaction mixture was dried, concentrated, and subjected to column chromatography to obtain a 95% isolated yield.
Example 50
Figure BDA0002654021170000233
To the reaction flask were added p-toluenesulfonyl fluoride (209.0mg, 1.2eq), HOBt (1.4mg, 0.01eq), p-phenylenediamine (108.1mg, 1mmol, 1.0eq), DMSO (1.25mL), DIPEA (350. mu.L, 2.0eq), 1,1,3, 3-tetramethyldisiloxane (355. mu.L, 2.0eq) and reacted at 25 ℃ for 24 hours. After the reaction, 70mL of ethyl acetate was added, washed with water three times, dried, concentrated, and subjected to column chromatography, with an isolation yield of 93%.
Example 51
Figure BDA0002654021170000241
To the reaction flask were added p-toluenesulfonyl fluoride (174.2mg, 1mmol, 1.0eq), HOBt (1.4mg, 0.01eq), p-anisidine (246.3mg, 2.0eq), DMSO (1.25mL), DIPEA (350. mu.L, 2.0eq), 1,1,3, 3-tetramethyldisiloxane (355. mu.L, 2.0eq) and reacted at 25 ℃ for 24 hours. After the reaction, 70mL of ethyl acetate was added, followed by washing with 15mL of water, 15mL of 1M hydrochloric acid, and 15mL of saturated saline, followed by drying, concentration, and column chromatography, and the isolation yield was 95%.
Example 52
Figure BDA0002654021170000242
P-Trifluoromethylphenoxysulfonyl fluoride (97.6mg, 0.4mmol, 2.0eq), HOBt (2.7mg, 0.1eq), α -methylbenzylamine (26.0. mu.L, 1.0eq), NMP (250. mu.L), DIPEA (35.0. mu.L, 1.0eq), 1,1,3, 3-tetramethyldisiloxane (71.0. mu.L, 2.0eq) were charged into a reaction flask and reacted at 0 ℃ for 12 hours. At the end of the reaction, the nuclear magnetic calculation yield was 90%.
Example 53
Figure BDA0002654021170000251
P-methoxyphenoxysulfonyl fluoride (49.5mg, 0.24mmol, 1.2eq), HOBt (1.4mg, 0.05eq), NMP (250. mu.L), DIPEA (35.0. mu.L, 1.0eq), 4-piperidone ethylene glycol (25.6. mu.L, 1.0eq), (TMS) were added to the reaction flask2O (85.0. mu.L, 2.0eq) was reacted at 60 ℃ for 24 hours. The yield was 100% by nuclear magnetic calculation.
Example 54
Figure BDA0002654021170000252
2, 6-Dimethylphenoxysulfonyl fluoride (81.7mg, 0.4mmol, 2.0eq), HOBt (1.4mg, 0.05eq), n-butylamine (20.0. mu.L, 1.0eq), DMSO (250. mu.L), DIPEA (35.0. mu.L, 1.0eq), 1,1,3, 3-tetramethyldisiloxane (71.0. mu.L, 2.0eq) were added to a reaction flask, and the mixture was reacted at 25 ℃ for 24 hours. The yield by nuclear magnetic calculation was 94%.
Example 55
Figure BDA0002654021170000253
To the reaction flask, p-dimethylaminophenoxysulfonyl fluoride (438.4mg, 2.0mmol, 2.0eq), HOBt (6.8mg, 0.05eq), tert-butylamine (105. mu.L, 1.0eq), DMSO (1.25mL), DIPEA (175. mu.L, 1.0eq), 1,1,3, 3-tetramethyldisiloxane (355. mu.L, 2.0eq) were added and reacted at 25 ℃ for 24 hours. After the reaction, 70mL of ethyl acetate is added, and the mixture is washed three times by 15mL of water, dried, concentrated and subjected to column chromatography, so that the separation yield is 91%.
Example 56
Figure BDA0002654021170000261
To the reaction flask were added p-methoxyphenoxysulfonyl fluoride (412.4mg, 2.0mmol, 2.0eq), HOBt (6.8mg, 0.05eq), 1-adamantanamine (151.3mg, 1.0eq), DMSO (1.25mL), DIPEA (175. mu.L, 1.0eq), 1,1,3, 3-tetramethyldisiloxane (355. mu.L, 2.0eq), and the mixture was reacted at 25 ℃ for 24 hours. After the reaction, 70mL of ethyl acetate and 15mL of 1M hydrochloric acid solution are added for washing twice, 15mL of water is used for washing once, and the mixture is dried, concentrated and subjected to column chromatography. The isolation yield was 93%.
Example 57
Figure BDA0002654021170000262
P-methoxyphenoxysulfonyl fluoride (412.4mg, 2.0mmol, 2.0eq), HOBt (6.8mg, 0.05eq), di-n-propylamine (101.2mg, 1.0eq), DMSO (1.25mL), DIPEA (175. mu.L, 1.0eq), 1,1,3, 3-tetramethyldisiloxane (355. mu.L, 2.0eq) were added to a reaction flask, and reacted at 25 ℃ for 24 hours. After the reaction, 70mL of ethyl acetate and 15mL of 1M hydrochloric acid solution are added for washing twice, 15mL of water is used for washing once, and the mixture is dried, concentrated and subjected to column chromatography. The isolation yield was 93%.
Example 58
Figure BDA0002654021170000263
P-iodophenoxysulfonyl fluoride (604.1mg, 2.0mmol, 2.0eq), HOBt (6.8mg, 0.05eq), diallylamine (123. mu.L, 1.0eq), DMSO (1.25mL), DIPEA (175. mu.L, 1.0eq), 1,1,3, 3-tetramethyldisiloxane (355. mu.L, 2.0eq) were added to the reaction flask and reacted at 25 ℃ for 24 hours. After the reaction, 70mL of ethyl acetate and 15mL of 1M hydrochloric acid solution are added for washing twice, 15mL of water is used for washing once, and the mixture is dried, concentrated and subjected to column chromatography. The isolation yield was 93%.
Example 59
Figure BDA0002654021170000271
To the reaction flask were added morpholine sulfonyl fluoride (40.6mg, 0.24mmol, 1.2eq), HOBt (27.0mg, 1.0eq), α -methylbenzylamine (26.0 μ L, 1.0eq), DMSO (250 μ L), DIPEA (70.0 μ L, 2.0eq), (TMS)2O (85.0. mu.L, 2.0eq) was reacted at 80 ℃ for 24 hours. The yield by nuclear magnetic calculation was 94%.
Example 60
The reaction was carried out in the same manner as in example 59 except that the amount of HOBt was changed to 0.3eq, and the nuclear magnetic calculated yield was 85%.
Example 61
Figure BDA0002654021170000272
Indolinesulfonyl fluoride (48.3mg, 0.24mmol, 1.2eq), HOBt (27.0mg, 1.0eq), morpholine (17.4. mu.L, 1.0eq), DMSO (250. mu.L), DIPEA (70.0. mu.L, 2.0eq), (TMS) were added to the reaction flask2O (85.0. mu.L, 2.0eq) was reacted at 80 ℃ for 15 hours. The nuclear magnetic calculation yield is 90%.
Example 62
Figure BDA0002654021170000281
To the reaction flask were added p-toluenesulfonyl fluoride (41.8mg, 0.24mmol, 1.2eq), HOBt (2.7mg, 0.1eq), p-cresol (21.6mg, 1.0eq), DMSO (250. mu.L), DIPEA (70.0. mu.L, 2.0eq), (TMS)2O (85.0. mu.L, 2.0eq) was reacted at 60 ℃ for 10 hours, and the nuclear magnetic calculation yield was 74%.
Example 63
Figure BDA0002654021170000282
2-thiophenesulfonyl fluoride (199.4mg, 0.24mmol, 1.2eq), HOBt (1.4mg, 0.01eq), benzhydrylamine (183.3mg, 1.0eq), DMSO (1.25mL), DIPEA (350. mu.L, 2.0eq), 1,1,3, 3-tetramethyldisiloxane (355. mu.L, 2.0eq) were added to the reaction flask, and the reaction was carried out at 25 ℃ for 24 hours. After the reaction is finished, the temperature is reduced to room temperature, 70mL of ethyl acetate is added, 15mL of water is washed for three times, and the reaction product is dried, concentrated and subjected to column chromatography, so that the separation yield is 94%.
Example 64
Figure BDA0002654021170000283
To the reaction flask were added camphorsulfonyl fluoride (56.2mg, 0.24mmol, 1.2eq), HOBt (20.0. mu.L, 0.01eq, 0.1M DMSO solution), α, α -dimethylbenzylamine (27.0mg, 1.0eq), DMSO (230. mu.L), DIPEA (70.0. mu.L, 2.0eq), 1,1,3, 3-tetramethyldisiloxane (71.0. mu.L, 2.0eq), and reacted at 25 ℃ for 24 hours. The nuclear magnetic calculation yield is 98%.
Example 65
Figure BDA0002654021170000291
To the reaction flask were added p-toluenesulfonyl fluoride (41.8mg, 0.24mmol, 1.2eq), HOBt (13.5mg, 0.5eq), mercaptobenzothiazole (33.5mg, 1.0eq), DMSO (250. mu.L), DIPEA (70.0. mu.L, 2.0eq), 1,1,3, 3-tetramethyldisiloxane (71.0. mu.L, 2.0eq) and reacted at 25 ℃ for 24 hours. And (3) identification result: ms (esi): 322.05[ M + H]+。
Example 66
Figure BDA0002654021170000292
To the reaction flask were added p-toluidine (0.43g, 4mmol, 1.0eq), HOBt (0.54g, 1.0eq), NMP (5.0mL), DIPEA (1.74mL, 2.5eq), and the mixture was reacted under reduced pressure with a sulfonyl fluoride balloon at 25 ℃ for 12 hours. And (3) identification result: ms (esi): 188.10[ M-H]-。
As described above, the catalyst or catalyst combination of the present invention is mild in reaction conditions and does not use expensive reagentsThe substance itself can efficiently make the substance contain-SO2The F group compound and the nucleophile undergo nucleophilic substitution reactions and can be adapted to a variety of-SO-containing compounds2Compounds of group F and nucleophiles, especially for use with low-activity-SO-containing compounds2A compound of group F and a nucleophilic reagent. As can be seen from the above comparative examples, for some of the compounds containing-SO2For nucleophilic substitution reactions of compounds of the F group, the reaction does not proceed at all without addition of the catalyst or catalyst composition of the present invention, and no target product is obtained. Without being bound by any theory, the inventors of the present invention have unexpectedly found that the catalyst or catalyst composition of the present invention is capable of sufficiently activating an SO-containing catalyst2Compounds of the group F, thereby enabling the inclusion of-SO2The compound of the F group and the nucleophile undergo nucleophilic substitution reaction with high efficiency. In addition, the method has simple and convenient reaction operation and high yield, and is suitable for large-scale production.

Claims (18)

1. A catalyst composition, comprising:
(a) at least one catalyst that is a compound of formula (I) or a compound of formula (II), or a combination thereof:
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，
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in the formulae (I) and (II), R1And R2Are each independently of the others selected from hydrogen, hydroxy, halogen, C1-C6Alkyl radical, NO2、C1-C6Alkoxy, amino, C1-C6Alkyl monosubstituted amino, C1-C6Alkyl-disubstituted amino, C1-C6Haloalkyl, C1-C6An alkyloxycarbonyl group; or R1And R2Together with the carbon atom to which they are attached form ring a;
the ring A is selected from: a monocyclic or compensated bicyclic aromatic ring having 6-10 carbon atoms; a monocyclic or compensated bicyclic heteroaryl ring having 5-10 ring atoms comprising 1-3 heteroatoms selected from N, O, S and any combination thereof; a monocyclic or fused bicyclic carbocycle having 3-10 carbon atoms; a monocyclic or compensated bicyclic heterocycle having 3-10 ring atoms comprising 1-3 heteroatoms selected from N, O, S and any combination thereof;
said ring A being optionally substituted by one or more than one substituent RaSubstituted, each substituent RaIdentical or different, independently of one another, from the group consisting of hydroxyl, halogen, C1-C18Alkyl radical, NO2、C1-C18Alkoxy, amino, C1-C6Alkyl monosubstituted amino, C1-C6Alkyl-disubstituted amino, C1-C6Haloalkyl, C1-C6Alkyl oxycarbonyl radical, C6-C10Aryl, benzyl;
R3are respectively selected from hydrogen, hydroxyl, sulfydryl, halogen and C1-C6Alkyl radical, NO2、C1-C6Alkoxy, amino, C1-C6Alkyl monosubstituted amino, C1-C6Alkyl-disubstituted amino, C1-C6Haloalkyl, C1-C18Alkyloxycarbonyl, oxytris (pyrrolidinyl) phosphonium hexafluorophosphate, oxytris (pyrrolidinyl) phosphonium tetrafluoroborate, oxytris (dimethylamino) phosphonium hexafluorophosphate, oxytris (dimethylamino) phosphonium tetrafluoroborate, oxydi (dimethylamino) carbonium hexafluorophosphate, oxydi (dimethylamino) carbonium tetrafluoroborate, oxydi (pyrrolidinyl) carbonium hexafluorophosphate, oxydi (pyrrolidinyl) carbonium tetrafluoroborate, -OSO2C1-C6Alkyl, -OSO2C1-C8Perfluoroalkyl group, -OSO2C6-C10An aryl group;
(b) at least one additive, wherein the additive is a silicon-containing compound selected from the group consisting of: unsubstituted or substituted trimethylsilyl, C1-C4Alkyl radical, C1-C4Haloalkyl, phenyl, C1-C4Alkoxy or any combination thereof mono-or poly-substituted silane;
unsubstituted or by C1-C4Alkyl radical, C1-C4Haloalkyl, phenyl, C1-C4Alkoxy or any combination thereof mono-or poly-substituted disiloxane;
a compound of formula (III)
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Wherein the substituent Re、Rf、Rg、Rh、Ri、Rj、RkIdentical or different, independently of one another, from hydrogen, C1-C4Alkyl radical, C1-C4Haloalkyl, phenyl, C1-C4An alkoxy group;
a compound of formula (IV)
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Wherein R isl、Rm、Rn、Ro、Rp、RqIdentical or different, independently of one another, from hydrogen, C1-C4Alkyl radical, C1-C4Haloalkyl, phenyl, C1-C4An alkoxy group;
a compound of formula (V)
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Wherein R isr、Rs、Rt、Ru、Rv、Rw、Rx、RyIdentical or different, independently of one another, from hydrogen, C1-C4Alkyl radical, C1-C4Haloalkyl, phenyl, C1-C4Alkoxy, n is 1 to 2000; and
(c) optionally a base, wherein the base is an organic base or an inorganic base,
the organic base is selected from: r11R12NR13WhereinR11、R12And R13Independently of one another, from hydrogen, C1-C4An alkyl group; r21R22N-Y-NR23R24Y is C1-C3Alkylene radical, R21、R22、R23And R24Independently of one another, from hydrogen, C1-C4An alkyl group; unsubstituted or substituted by halogen, C1-C4Alkyl-substituted diaza or triazabicyclo C6-C12An olefin;
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、
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、
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、
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、
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、
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、
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、
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、
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、
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、
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、
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(ii) a And
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wherein R is41、R42、R43、R44、R45Independently of one another, from hydrogen, C1-C4An alkyl group;
the inorganic base is selected from carbonates, phosphates, hydrides and C of alkali metals or alkaline earth metals1-C18An alkyl oxide.
2. The catalyst composition of claim 1, wherein the compound of formula (V)
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And n is 10-1000.
3. The catalyst composition of claim 1, wherein the compound of formula (V)
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And n is 100-500.
4. The catalyst composition of claim 1, wherein in the compound of formula (I) or formula (II), R1And R2Are each independently of the other selected from hydrogen, C1-C6Alkyl radical, C1-C6Alkoxy radical, C1-C6Haloalkyl, C1-C6An alkyloxycarbonyl group; or R1And R2Together with the carbon atom to which they are attached form ring a;
the ring A is selected from: a monocyclic or compensated bicyclic aromatic ring having 6-10 carbon atoms; a monocyclic or compensated bicyclic heteroaryl ring having 5-10 ring atoms comprising 1-3 heteroatoms selected from N, O, S and any combination thereof;
said ring A being optionally substituted by one or more than one substituent RaSubstituted, each substituent RaIdentical or different, independently of one another, from the group consisting of hydroxyl, halogen, C1-C18Alkyl radical, NO2、C1-C18Alkoxy, amino, C1-C6Alkyl monosubstituted amino, C1-C6Alkyl-disubstituted amino, C1-C6Haloalkyl, C1-C6Alkyl oxycarbonyl radical, C6-C10Aryl, benzyl;
R3are respectively selected from hydrogen, hydroxyl, sulfydryl, halogen and C1-C6Alkyl radical, NO2、C1-C6Alkoxy, amino, C1-C6Alkyl monosubstituted amino, C1-C6Alkyl-disubstituted amino, C1-C6Haloalkyl, C1-C18Alkyloxycarbonyl, oxytris (pyrrolidinyl) phosphonium hexafluorophosphate, oxytris (pyrrolidinyl) phosphonium tetrafluoroborate, oxytris (dimethylamino) phosphonium hexafluorophosphate, oxytris (dimethylamino) phosphonium tetrafluoroborate, oxydi (dimethylamino) carbonium hexafluorophosphate, oxydi (dimethylamino) carbonium tetrafluoroborate, oxydi (pyrrolidinyl) carbonium hexafluorophosphate, oxydi (pyrrolidinyl) carbonium tetrafluoroborate, -OSO2C1-C6Alkyl, -OSO2C6-C10And (4) an aryl group.
5. The catalyst composition of claim 1, wherein in the compound of formula (I) or formula (II), R1And R2Are each independently of the other selected from hydrogen, C1-C6An alkyloxycarbonyl group; or R1And R2Together with the carbon atom to which they are attached form ring a;
the ring A is selected from: a benzene ring or a naphthalene ring; a monocyclic or compensated bicyclic heteroaryl ring having 5-10 ring atoms comprising 1 heteroatom selected from N, O, S;
said ring A being optionally substituted by one or more than one substituent RaSubstituted, each substituent RaIdentical or different, independently of one another, from the group consisting of hydroxyl, halogen, C1-C18Alkyl radical, NO2、C1-C18Alkoxy, amino, C1-C6Alkyl monosubstituted amino, C1-C6Alkyl-disubstituted amino, C1-C6Haloalkyl, C1-C6Alkyl oxycarbonyl radical, C6-C10Aryl, benzyl;
R3are respectively selected from hydrogen, hydroxyl, sulfydryl, halogen and C1-C6Alkyl radical, NO2、C1-C6Alkoxy, amino, C1-C6Alkyl monosubstituted amino, C1-C6Alkyl-disubstituted amino, C1-C6Haloalkyl, C1-C18Alkyloxycarbonyl, oxytris (pyrrolidinyl) phosphonium hexafluorophosphate, oxytris (pyrrolidinyl) phosphonium tetrafluoroborate, oxytris (dimethylamino) phosphonium hexafluorophosphate, oxytris (dimethylamino) phosphonium tetrafluoroborate, oxydi (dimethylamino) carbonium hexafluorophosphate, oxydi (dimethylamino) carbonium tetrafluoroborate, oxydi (pyrrolidinyl) carbonium hexafluorophosphate, oxydi (pyrrolidinyl) carbonium tetrafluoroborate, -OSO2C1-C6Alkyl, -OSO2C6-C10And (4) an aryl group.
6. The catalyst composition of any one of claims 1-5, wherein the additive is selected from the group consisting of C1-C3Alkyl radical, C1-C2Alkoxy or phenyl or any combination thereof; quilt C1-C4Alkyl or phenyl or any combination thereof; a compound of formula (III) wherein the substituent Re、Rf、Rg、Rh、Ri、Rj、RkIdentical or different, independently of one another, from hydrogen, C1-C4An alkyl group; a compound of formula (IV), whichIn Rl、Rm、Rn、Ro、Rp、RqIdentical or different, independently of one another, from hydrogen, C1-C4An alkyl group; a compound of formula (V) wherein Rr、Rs、Rt、Ru、Rv、Rw、Rx、RyIdentical or different, independently of one another, from hydrogen, C1-C4An alkyl group.
7. The catalyst composition of claim 6, wherein the additive is selected from any one of the following compounds or any combination thereof:
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Figure DEST_PATH_IMAGE021
silica, silica gel, C3H9OSi·(CH4OSi)n·C3H9Si, wherein n is 1 to 2000.
8. The catalyst composition of claim 7, wherein C3H9OSi·(CH4OSi)n·C3H9In Si, n is 10-1000.
9. The catalyst composition of claim 7, wherein C3H9OSi·(CH4OSi)n·C3H9In Si, n is 100-500.
10. The catalyst composition of any one of claims 1-5, wherein the catalyst composition is for catalyzing reactants: containing-SO2F, with nucleophilic substitution by a nucleophile, in which case the catalyst: the molar ratio of the reactants is 1: 20000 to 1: 1; silicon-containing compound additive: the molar ratio of the reactants is 1: 20 to 20: 1; when the nucleophile is an amine and is in excess relative to the reactants, the base (c) may be absent, when the nucleophile is not an amine or is not in excess relative to the reactants even if the nucleophile is an amine, the base (c) needs to be added, and the base (c): the molar amount of the catalyst is more than 0.2: 1.
11. The catalyst composition of claim 10, wherein the catalyst: the molar ratio of the reactants is 1: 2000 to 1: 1.
12. the catalyst composition of claim 10, wherein the catalyst: the molar ratio of the reactants is 1: 200 to 1: 1.
13. the catalyst composition of claim 10, wherein the silicon-containing compound additive: the molar ratio of the reactants is 1: 10 to 10: 1.
14. the catalyst composition of claim 10, wherein the silicon-containing compound additive: the molar ratio of the reactants is 1: 5 to 5: 1.
15. the catalyst composition of any one of claims 1-5, wherein the organic base is selected from R11R12NR13Wherein R is11、R12And R13Independently of one another, from C1-C4An alkyl group; r21R22N-Y-NR23R24Y is ethylene, R21、R22、R23And R24Independently of one another, from hydrogen, C1-C4An alkyl group; unsubstituted diaza or triazabicyclo C6-C12An olefin;
Figure 748323DEST_PATH_IMAGE006
、
Figure 757867DEST_PATH_IMAGE022
、
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、
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、
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、
Figure 251351DEST_PATH_IMAGE026
、
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、
Figure 760699DEST_PATH_IMAGE028
、
Figure 698568DEST_PATH_IMAGE014
、
Figure DEST_PATH_IMAGE029
、
Figure 478436DEST_PATH_IMAGE030
、
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(ii) a And
Figure 358405DEST_PATH_IMAGE032
wherein R is41、R42、R43、R44、R45Independently of one another, from C1-C4An alkyl group;
the inorganic base is selected from alkali metal carbonates or phosphates.
16. The catalyst composition of any one of claims 1-5, wherein the base is selected from triethylamine, diisopropyldiethylamine, 1, 8-diazabicyclo [5.4.0] undec-7-ene (DBU), 1,5, 7-triazabicyclo [4.4.0] dec-5-ene (TBD), 1, 4-diazabicyclo [2.2.2] octane (DABCO), potassium carbonate, cesium carbonate, potassium phosphate, 2-tert-butylimino-2-diethylamino-1, 3-dimethylperhydro-1, 3, 2-diazaphosphorus (BEMP), and 2-tert-butyl-1, 1,3, 3-tetramethylguanidine (Barton base).
17. The catalyst composition of any one of claims 1-5, wherein the base is triethylamine or diisopropylethylamine.
18. Use of the catalyst composition of any of claims 1-17 for catalyzing an-SO-containing catalyst as shown below2The use of a compound of the F group for nucleophilic substitution reaction with a nucleophile,
Figure DEST_PATH_IMAGE033
。
CN202010880701.4A 2020-08-27 2020-08-27 Catalyst composition and use of catalyst composition or catalyst for catalyzing nucleophilic substitution reaction Active CN112121852B (en)

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