WO2006032780A1 - Macrocyclic chiral complexes useful as catalysts - Google Patents

Abstract

The invention concerns compounds of formula (I) and their use as catalyst.

Description

 MACROCYCLIC CHIRAL COMPLEXES USEFUL AS CATALYSTS.

The need to market an optically pure form of drugs with one or more centers of chirality has led to the development of novel chiral ligand catalysts capable of producing enantiomerically pure forms of synthons useful in the synthesis of drugs ( I. Ojima, Catalytic Asymmetric Synthesis, Wiley-VCH, New York, ^2nd edition, 2000). The development of biomimetic catalysis over the past 25 years has led to the development of metal complexes capable of transferring oxygen, nitrogen or carbon atoms to suitable substrates (olefins or alkanes) via active species of metal-oxo, metal-nitrene or metal-carbene type. Similarly asymmetric metal complexes catalyze the enantioselective hydrolysis of epoxides or the formation of chiral lactones via a Baeyer-Villiger reaction (for two recent reviews, see EN Jacobsen et al., In Comprehensive Asymmetric Catalysis, EN Jacobsen, A. Pfaltz , H. Yamamoto, Eds, Springer: New York, 1999, Vol.I, 649 and T. Katsuki, Synlett, 2003, 281).

Among the various asymmetric reactions catalyzed by transition metals, asymmetric epoxidation has been the most studied because it allows to obtain optically pure epoxides very useful in organic synthesis. Among the success stories in this area are the asymmetric epoxidation of allylic alcohols using a titanium complex ligated with a tartrate (Sharpless-Katsuki catalyst) and the asymmetric epoxidation of simple-to-use olefins. using a manganese complex having a chiral Schiff base (Salen ligand) as a ligand (Jacobsen-Katsuki catalyst). In fact, this last catalyst capable of transferring the oxygen atom from NaOCI to an olefin is the asymmetric version of a reaction invented in the early 1980s (B. Meunier et al., J. Amer Chem Soc, 1984 , 106, 6668).

The weak point of these metal catalysts comprising a chiral Schiff base is the low stability of the complexes in strongly oxidizing media (sodium hypochlorite, peroxides, etc.). Also, an object of this The invention is to provide novel macrocyclic Schiff base type chiral ligands capable of catalyzing, via suitable metal complexes, transfers of oxygen, nitrogen or carbon atoms or even to open epoxides or form lactones. from ketones. The strategy developed to prepare these novel catalysts was to make basic Schiff macrocycles by connecting the 3 and 3 'positions of the ligands using different bonds, taking care not to break the ligand symmetry C ₂ , a characteristic essential of many chiral metal catalysts. The general formula (I) below describes the compounds that are the subject of the application. Several preparations of chiral ligands have been made and these ligands have been complexed by a metal ion. These various compounds are described below and are also part of the present invention. According to another object of the present invention, the catalytic properties of these complexes have been demonstrated, in particular by studying their activity in the case of asymmetric epoxidation (manganese complex associated with an oxygen atom donor, NaOCI , PhIO ₁ H ₂ O ₂ , n-Bu ₄ HSO ₅ , m-CPBA).

The present invention relates to the chiral compounds of formula (I):

(I) as well as the resulting mono-cationic complex, and optionally with its mono-anionic counterion.

In the general formula (I): "M represents a metal atom or a salt of this atom, in particular a group IB, HB, IHB, IVB, VB, VIB, VIIB, VIIIB or IHA atom; preferably an atom selected from the following atoms: Sc, Ti, Zr, V, Nb, Cr, Mo, Mn, Fe, Ru, Co, Sc, Ni, Cu, Zn, Cd, Al, Ga, In, or a their salts; L represents a neutral or anionic ligand;

- A and A ', chiral, identical or different, independently represent a chain of type (-CR8 _a R9 _a -) a and (-CR8' _{a '} R9' _a -) a 'respectively, where: is R8 _a and R9 _a and R8V and R9 ' _a ' are the same or different for each linkage (-CR8 _to R9 _a -) a and (-CR8 ' _a ' R9 ' _a -) a', and independently represent a hydrogen atom, a group aryl or heteroaryl, or is _R8 and R8 _'has, respectively R9 _is and R9 _has taken together with the carbon atoms to which they are attached a cycloalkyl group and R 9 _a and R 9' _{a \} R8 respectively _a and R8V represent an atom hydrogen, or either two of _R8 and / or R9 _is consecutive, respectively R8 _'has and / or R9' consecutive _has taken together with the carbon atoms to which they are attached form an optionally substituted aryl group, and wherein a and a ', identical or different represent an integer chosen from 1 or 2; preferably, A and A 'represent a link of the type:

respectively, or their enantiomers,

or a link of type:

respectively, as

their enantiomers

R8, R9 and R8 'and R9' are the same or different, and independently represent a hydrogen atom, an aryl or heteroaryl group, or R8 and

R8 ', respectively R9 and R9' together with the carbon atoms to which they are attached form a cycloalkyl group and R9 and R9 ', respectively R8 and R8' represent a hydrogen atom, and

R12, R12 ', R13, R13', which may be identical or different, independently represent a hydrogen or halogen atom or an alkyl group;

R14, R14 ', R15, R15, R16, R16', R17, R17 ', which may be identical or different, represent a hydrogen atom or R12 and R13, respectively R12' and R13 ', R14 and R15, respectively R14' and R15 ', or R16 and R17, respectively R16 'and

R17 'together with the carbon atoms to which they are attached form an aryl or heteroaryl group.

R4, R4 ', R6, R6', which may be identical or different, independently represent a hydrogen atom, a halogen atom or a group -NO ₂ , -O-alkyl, -aryl, or

-alkyl optionally substituted with one or more groups selected from halogen atoms and -OR, -CN, -NO ₂ , -NRR ', -COOR, perhaloalkyl, -aryl;

R5, R5 ', which may be identical or different, independently represent a halogen atom or a group -NO ₂ , -O-alkyl, -aryl, or -alkyl optionally substituted with one or more groups chosen from halogen atoms and - OR, -CN, -NO ₂ , -NRR ', -COOR, perhaloalkyl, -aryl;

m, m ', which are identical or different, represent O or 1;

- R10, R11, R10 ', R11' identical or different independently represent a hydrogen atom or a group selected from -alkyl, -aryl each optionally substituted by one or more halogen atoms;

- W and W, identical or different independently represent an oxygen atom or a group -NR-, -CRR'-, -SiRR'-; X represents an alkyl chain of 1 to 10 carbon atoms, preferably linear, optionally interrupted by one or more oxygen atoms or by one or more aryl groups, such as - alkyl-O-alkyl-, -alkyl- O-alkyl-O-alkyl-, etc., or -alkyl-aryl-alkyl-, -alkyl-aryl-alkyl-aryl-alkyl-, etc., where the alkyl chain is optionally perhalogenated, and wherein the aryl group is optionally substituted by one or more substituents, which may be identical or different, chosen from -OH, -O-alkyl, -COOR, -NRR ', -SO ₃ H, -S (O) pR, -NO ₂ , -CN;

- p = 0, 1 or 2;

R and R ', which may be identical or different, independently represent a hydrogen atom or an -alkyl group, optionally substituted with one or more substituents, which may be identical or different, chosen from -OR, -COOR, -NRR', -SO ₃ H, -S (O) pR, -NO ₂ , -CN; More specifically, when L represents a neutral ligand, the complex has a resulting positive charge. The product of formula (I) can then also include the counterion to compensate for the charge of the monocatalytic complex. As a counterion, there may be mentioned in particular the monoanionic species usually used, such as halides, such as CI ^" , tosylate, acetate, BF ₄ ^" , PFβ ^" ions, etc.

Preferably, R4 and R4 \ R5 and R5 ', R6 and R6 \ R7 and R7 \ R8 and R8 \ R9 and R9 \ R10 and R10', R11 and R11 ', R12 and R12', R13 and R13 \ R14 and R14 ', R15 and R15', R16 and R16 \ R17 and R17 "are 2 to 2.

Preferably, M represents a metal atom of group VIIB, or VIIIB, more preferably Mn or Co.

Preferably, L represents a halogen atom, more preferably chlorine, or a neutral ligand, especially chosen from 4-phenylpyridine N-oxide, 4-tert-butylpyridine or N-morpholine oxide.

Preferably, (A) a and (A ') a', which are identical, each represent a link of the type:

respectively, or their enantiomers, or the compounds of formula (I ¹ )

or their enantiomers, as well as the resulting mono-cationic complex, and optionally with its mono-anionic counter-ion, where

R8 and R8, respectively R9 and R9 \ are identical to an aryl or heteroaryl group, or R8 and R8 ', respectively R9 and R9' form together with the carbon atoms to which they are attached a cycloalkyl group and R9 and R9 \ respectively R8 and R8 'represent a hydrogen atom, or a link of type:

chiral respectively, or the compounds of formula (I ")

chirals, such as

or their enantiomers as well as the resulting mono-cationic complex, and optionally with its mono-anionic counter-ion, where R12, R12 \ R13, R13 'represent a hydrogen atom; R14, R14 ', R15, R15', R16, R16 ¹ R17, R17 'represents a hydrogen atom.

The compounds of formula (I ') are particularly preferred. More preferably, (A) a and (A ') a', which are identical, each represent a

link of type:

or their enantiomers where R8, R8 ', R9, R9' are defined as above.

Even more preferably, R8 and R8 ', respectively R9 and R9 \ identical represent a phenyl group and R9 and R9', respectively R8 and R8 'represent a hydrogen atom, or, even more preferably, R8 and R8', respectively R9 and R9 together form a cycloalkyl and R9 and R9 ', respectively R8 and R8' represent a hydrogen atom.

Preferably, R4, R4 ', R6, R6' represent a hydrogen atom. Preferably, R5 and R5 ', which are identical, represent an alkyl group; more preferably, R5 and R5 'represent a tert-butyl group. More preferably, m = m '= 1.

Preferably, R10, R11, R10 ', R11' which are identical represent a group chosen from -alkyl, -aryl each optionally substituted with one or more halogen atoms; more preferably, R10, R11, R10 ', R11 ¹ represent a methyl group or a phenyl group substituted by a halogen atom. Preferably, W and W ₁ identical represent an oxygen atom.

Preferably, X represents a chain -alkyl-O-alkyl-, -alkyl-O-alkyl-O-alkyl-, etc. or -alkyl-aryl-alkyl-, -alkyl-aryl-alkyl-aryl-alkyl-, etc. . wherein the aryl group is optionally substituted with -OH. More preferably, X represents a chain -Et-O-Et- or -Me-Ph (OH) -Me-.

According to the present invention, the alkyl radicals represent saturated hydrocarbon radicals, in straight or branched chain, of 1 to 20 carbon atoms, preferably of 1 to 5 carbon atoms.

Mention may in particular be made, when they are linear, the methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, dodecyl, hexadecyl and octadecyl radicals.

When they are branched or substituted by one or more alkyl radicals, mention may be made especially of the isopropyl, tert-butyl, 2-ethylhexyl, 2-methylbutyl, 2-methylpentyl, 1-methylpentyl and 3-methylheptyl radicals. Perhaloalkyl means an alkyl group in which all the hydrogen atoms have been replaced by a halogen atom. Particularly preferred are perfluoroalkyl groups such as -CF ₃ . The alkoxy radicals according to the present invention are radicals of formula -O-alkyl, the alkyl being as defined previously.

Among the halogen atoms, mention is made more particularly of fluorine, chlorine, bromine and iodine atoms, preferably fluorine. The alkenyl radicals represent hydrocarbon radicals, in straight or linear chain, and comprise one or more ethylenic unsaturations. Among the alkenyl radicals, mention may especially be made of allyl or vinyl radicals. The alkynyl radicals represent hydrocarbon radicals, in straight or linear chain, and comprise one or more acetylenic unsaturations. Among the alkynyl radicals, there may be mentioned acetylene.

The cycloalkyl radical is a saturated or partially unsaturated, non-aromatic, mono-, bi- or tricyclic hydrocarbon radical of 3 to 10 carbon atoms, such as in particular cyclopropyl, cyclopentyl, cyclohexyl or adamantyl, as well as the corresponding rings containing one or more unsaturations. Aryl means a hydrocarbon aromatic system, mono or bicyclic

6 to 10 carbon atoms.

Among the aryl radicals, there may be mentioned the phenyl or naphthyl radical.

Among the -alkyl-aryl radicals, there may be mentioned the benzyl or phenethyl radical.

The heteroaryl radicals denote aromatic systems comprising one or more heteroatoms chosen from nitrogen, oxygen or sulfur, mono or bicyclic, of 5 to 10 carbon atoms. Among the heteroaryl radicals, mention may be made of pyrazinyl, thienyl, oxazolyl, furazanyl, pyrrolyl, 1,2,4-thiadiazolyl, naphthyridinyl, pyridazinyl, quinoxalinyl, phthalazinyl and imidazo [1]. , 2-a] pyridine, rimidazo [2,1-b] thiazolyl, cinnolinyl, triazinyl, benzofurazanyl, azaindolyl, benzimidazolyl, benzothienyl, thienopyridyl, thienopyrimidinyl, pyrrolopyridyl, imidazopyridyl, benzoazaindole, 1,2,4-triazinyl, benzothiazolyl, furanyl, imidazolyl, indolyl, triazolyl, tetrazolyl, indolizinyl, isoxazolyl, isoquinolinyl, isothiazolyl, oxadiazolyl , pyrazinyl, pyridazinyl, pyrazolyl, pyridyl, pyrimidinyl, purinyl, quinazolinyl, quinolinyl, isoquinolyl, 1,3,4-thiadiazolyl, thiazolyl, triazinyl, isothiazolyl, carbazolyl and the corresponding groups resulting from their fusion or from the fusion with the phenyl ring. Preferred heteroaryl groups include thienyl, pyrrolyl, quinoxalinyl, furanyl, imidazolyl, indolyl, isoxazolyl, isothiazolyl, pyrazinyl, pyridazinyl, pyrazolyl, pyridyl, pyrimidinyl and quinazolinyl. quinolinyl, thiazolyl, carbazolyl, thiadiazolyl, and groups derived from the fusion with a phenyl ring, and more particularly quino lynyl, carbazolyl, thiadiazolyl.

In particular, the compounds according to the invention corresponding to the formula

as well as the resulting mono-cationic complex, and optionally with its mono-anionic counterion where (A) a and (A ') a', chiral, identical, each represent a link of

type:

or their enantiomers, ie the compounds of formula (I ¹ ):

or their enantiomers, as well as the resulting mono-cationic complex, and optionally with its mono-anionic counter-ion, where R8, R8 ', R9, R9' are defined as previously.

As preferred compounds according to the invention, mention may notably be made of the following compounds:

as well as the resulting mono-cationic complex, and optionally with its mono-anionic counterion; more preferably:

; even more preferentially

as well as the resulting mono-cationic complex, and optionally with its mono-anionic counterion.

According to one advantageous aspect, the compounds according to the invention are chiral, because of the stereochemistry of the radicals A and A ', especially when A and A' represent a link of type:

respectively, or their enantiomers or a link of type:

chiral respectively, or their enantiomers, where, in the latter case, the chiraiity is ensured because of the presence of the naphthyl group which blocks the stereochemistry of the molecule.

According to another object, the present invention also relates to the process for preparing the compounds of formula (I) according to the invention.

The compounds of general formula (I) may be prepared by application or adaptation of any method known per se of and / or to those of ordinary skill in the art, in particular those described by Larock in Comprehensive Organic.

Transformations, VCH Pub., 1989, or by application or adaptation of the methods described in the examples which follow.

In the reactions described below, it may be necessary to protect the reactive functional groups, for example the hydroxy, amino, imino, thio, carboxy groups, when desired in the final product, to avoid their undesirable participation in the reactions. Traditional protection groups can be used in accordance with standard practice, for examples see T. W. Greene and P.G.M. Wuts in Protective Groups in Organic Chemistry, John Wiley and Sons, 1991; J.F.W. McOmie in Protective Groups in

Organic Chemistry, Plenum Press, 1973.

The compounds of formula (I) can be obtained from the corresponding compounds of formula (II):

(H) wherein R4, R5, R6, R10, R11, W, R4 \ R5 ', R6', R10 ', R11 ^1, W, X are as defined in formula (I), by reacting a compound of formula (III):

(A) a (A ') a'

NH. NH,

(III) wherein A, a, A ', a' are as defined in formula (I), optionally in the presence of a salt of M. The salt of M can be anhydrous or hydrated. Preferably, when M is Mn, manganese (II) diacetate tetrahydrate is used.

Preferably, this reaction is carried out in a solvent medium such as ethanol or methanol, with stirring, preferably at room temperature, under an inert atmosphere, then in the presence of oxygen. When operating in the absence of M salt, the non-metallated free Schiff base is obtained which can be isolated and purified. The metallation is then carried out with M, for example in refluxing ethanol in the presence of sodium methanolate (MeONa) or in DMF at 120 ^° C. in the presence of 1,5-diazabicyclo [4.3.0] non-5- ene (DBN). More precisely, when the diamine (III) is bis- (2-naphthylamine), the metallation with M is carried out in a separate step as discussed above.

The method according to the invention may also comprise the subsequent step of isolating and / or purifying the product of formula (I) obtained at the end of this reaction. The compounds of formula (III) are commercially available or may be prepared by application or adaptation of methods known per se, within the abilities of those skilled in the art.

The compounds of formula (II) may be prepared by one or other of the following routes:

According to a first alternative, when m = 0, the compounds of formula (II) can be obtained from each of the compounds (V) and (V):

in which R4, R5, R6, W, R4 ', R5, R6', W are as defined in formula (I), in the presence of compound (IV):

(IV) wherein X is defined as in general formula (I) and Gp and Gp 'represent a leaving group.

Any group leaving within man's reach may be suitable; preferentially, Gp and Gp 'represent the tosylate group (Gp = Gp' = -OTs).

Preferably, one operates in the presence of an equivalent of each of the compounds (V) and (V) for one equivalent of the compound of formula (IV).

Preferably, this reaction is carried out in a solvent medium, such as DMSO, DMF, THF, acetonitrile or acetone with stirring, preferably at a temperature of between 0 ^° C. and room temperature, under an inert atmosphere, presence of a base, such as NaH, Cs ₂ CO ₃ or K ₂ CO ₃ , then by acidification of the reaction mixture. The compounds of formula (IV) are commercially available or may be prepared by application or adaptation of methods known per se, within the abilities of those skilled in the art, in particular by application or adaptation of the method described by Cornforth et al, Tetrahedron 1973 , 29, 1659.

The compounds of formula (V) and (V) may be prepared from compounds of formula (VI) and (VI '):

(Vl) (Vl ')

wherein R4, R5, R6, W, R4 ', R5, R6', W are as defined in formula (I), in the presence of chloroform and a base, such as a mineral base, especially NaOH.

Preferably, this reaction is carried out in a solvent medium such as methanol in an aqueous medium, with stirring, preferably keeping the reaction medium at a temperature between 0 ^° C. and room temperature and then by acidifying the reaction mixture.

According to a second alternative, when m = 1, the compounds of formula (II) can be obtained from the compounds of formula (VII):

Wherein R4, R5, R6, R10, R11, W, R4 ', R5, R6', R10 ', R11', W, X are as defined in formula (I) and R "represents a group Preferably, R "is an allyl group. Preferably, the deprotection is carried out in the presence of a catalyst such as a palladium catalyst, in particular Pd (PPh ₃ ) _4. , In a basic medium, in particular in the presence of a mineral base such as K ₂ CO ₃ , or NaBH ₄ , in a solvent medium such as MeOH or THF, with stirring.

The compound of formula (VII) can be obtained from a compound of formula (VIII):

Wherein R 4, R 5, R 6, R 10, R 11, W, R 4, R 5, R 6, R 10, R 11, W ₁ X, R "are as defined in formula (VII) and halogen atom, especially bromine, by a formylation reaction The reaction is preferably carried out with DMF.

Preferably, tetramethylethylenediamine (TMEDA) or any other suitable equivalent reagent is used in the presence of a base, such as n-BuLi or tert-BuLi. Preferably, the reaction is carried out in a solvent medium such as ether, while maintaining the temperature of the reaction medium at a low temperature, for example between -90 ^° C. and -50 ^° C., preferably with stirring and under an inert atmosphere.

The compound of formula (VIII) is obtained from compounds of formula

(IX) and (IX '):

(IX) (IX ') wherein R4, R5, R6, R10, R11, _W1 R4 ', R5 ^1, R6', R10 ', R11 \ W', R ', Hal are as defined in formula (VIII) and the compound ( IV):

(IV) wherein X is defined as in general formula (I) and Gp and Gp 'represents a leaving group.

Any group leaving within man's reach may be suitable; preferentially, Gp and Gp 'represent the tosylate group (Gp = Gp' = -OTs). Preferably, one operates in the presence of an equivalent of each of the compounds (IX) and (IX ') for an equivalent of (IV).

Preferably, this reaction is carried out with stirring, preferably at room temperature, under an inert atmosphere, in the presence of a base, such as

NaH, CS ₂ CO ₃ or K ₂ CO ₃ by adding the compounds (IX) and (IX ') in a solvent medium such as THF, DMF, DMSO, acetonitrile or acetone, and then adding the compound (IV) in a solvent medium such as DMF, DMSO or THF.

The compounds of formula (IX) and (IX ') may be prepared from compounds of formula (X) and (X'):

(X) (X ') wherein R4, R5, R6, Ha, R ", R4', R5 ', R6' are as defined in formula (IX) and compounds of formula (XI) and (XI ') ):

R10R11-C = O and R10'R1 T-C = O (XI) (X1 ') in the presence of nBuϋ.

Preferably, to a solution of the compounds (X) and (X ') in a solvent medium such as diethyl ether or THF, the nBuLi is added with stirring. in a solvent medium such as hexane, pentane or cyclohexane, and then compounds (Xl) and (Xl ') preferably maintaining the reaction medium at low temperature, about -78 ° C.

The compounds of formula (Xl) and (Xl ') can be prepared from compounds of formula (XII) and (XII'):

(XII) (XII ')

in which R4, R5, R6, Ha1, R4 ', R5', R6 'are as defined in formula (X), by the action of a compound of formula: R "-Gp" (XIII) where R "is as defined in formula (X) and Gp "represents any leaving group within the reach of those skilled in the art, preferably a halogen atom, preferably bromine.

Preferably, one operates in a solvent medium such as dichloromethane / water or DMF, in the presence of n-Bu ₄ NOH or NaH respectively.

The compounds of formula (XII) and (XII ') may be prepared from compounds of formula (XIV) and (XIV):

(XIV) (XIV)

in which R4, R5, R6, R4 ', R5', R6 'are as defined in formula (XIII), by the action of a compound of formula HaI ₂ where HaI is as defined in formula (XII). Preferably, one operates in an acid medium, for example acetic acid, in the presence of a salt such as sodium acetate.

The compounds of formula (XIV) and (XIV) are commercially available or may be prepared by application or adaptation of methods known per se, within the abilities of those skilled in the art, in particular by application or adaptation of the method described by Chang and al, J. Org. Chem. 1996, 61, 8414-8418.

The compounds thus prepared can be recovered from the reaction mixture by conventional means. For example, the compounds can be recovered by distilling the solvent from the reaction mixture or if necessary after distilling the solvent from the solution mixture, pouring the remainder into water followed by extraction with an organic solvent immiscible in the reaction mixture. water, and distilling the solvent from the extract. In addition, the product may, if desired, be further purified by various techniques, such as recrystallization, reprecipitation or various chromatography techniques, including column chromatography or preparative thin layer chromatography.

The ligand L can be modified by placing the compound of formula (I) in solution in the appropriate solvent, for example dichloromethane, so as to introduce the desired neutral ligand (for example, 4-PPNO, 4-tBuPy, NMO).

According to an advantageous aspect, the nature of the ligand made it possible to modulate the activity of catalysts of the compounds of formula (I). According to another advantageous aspect, the compound (I) with the desired ligand can be formed in situ by adding the ligand to the reaction mixture containing the reagents of the reaction to be catalyzed (for example the olefin and the oxidizing agent) and the compound (I) (optionally linked to a ligand to be replaced). As a ligand, 4-PPNO is preferred.

According to another object, the present invention also relates to the use of the compounds of formula (I) as a catalyst. According to a preferred aspect, the catalysts according to the invention can catalyze reactions of transfer of oxygen, nitrogen or carbon atoms, opening of epoxides, or formation of lactones from ketones.

According to a more preferred aspect, mention may be made of epoxidation reactions, asymmetric opening of epoxides or reactions of Baeyer Villiger; more preferably, the epoxidation reactions.

According to another object, the present invention therefore also relates to an olefin epoxidation process comprising reacting said olefin, an oxidizing agent and a compound of formula (I), optionally in the presence of a ligand, such as those previously mentioned.

According to a preferred aspect, the compound (I) is used as a catalyst at concentrations of between 0.05 and 10 mol%, preferably 5 mol%. According to another preferred aspect, there may be mentioned as oxidizing agent any agent usually used to form epoxides, such as NaOCI, PhIO, nBu ₄ NHSO ₅ , mCPBA, H ₂ O ₂ .

According to another object, the present invention also relates to a composition comprising an olefin, an oxidizing agent as defined above and a compound of formula (I), and optionally a ligand, such as those mentioned above.

According to these objects, M is preferably a group VIIB metal atom, such as Mn.

According to another object, the present invention therefore also relates to an epoxide opening process comprising reacting said epoxide, water and a compound of formula (I), optionally in the presence of a ligand, such as than those previously mentioned.

According to another object, the present invention also relates to a composition comprising an epoxide, water, a compound of formula (I), and optionally a ligand, such as those mentioned above. According to this object, M is preferably a metal atom of Group VIIIB ₁ as Co.

According to another object, the present invention therefore also relates to a Bayer-Villiger process comprising the reaction of a ketone, a peracid and a compound of formula (I), optionally in the presence of a ligand, such as those previously mentioned.

According to a preferred aspect, the compound (I) is used as a catalyst at concentrations of between 0.05 and 10 mol%, preferably 5 mol%.

According to another object, the present invention also relates to a composition comprising a ketone, a peracid and a compound of formula (I), and optionally a ligand, such as those mentioned above.

According to these objects, M is preferably a Group VIIIB metal atom, such as Co.

The following examples represent an illustration of the invention; they should not be considered as a limitation of this invention and the claims below.

1 - Preparation of the Catalysts Example A: Preparation of the complex 3

1 + 1/2 OT; , NaH _5s DMSO

2,3-Dihydroxy-5-tert-butylbenzaldehyde 1

To a solution of 4-tert-butylcatechol (15 g, 1.15 mmol) in 45 ml of methanol and NaOH (46 g, 1.15 mmol) in 40 ml of water is added dropwise 100 ml of chloroform ( 1.25 mmol) under strong mechanical stirring for 1 h 30 min. The reaction is very exothermic and the temperature must be maintained at 30 ^° C. using a cold water bath. After complete addition of chloroform, the solution is stirred for 2 h at room temperature and then acidified to pH = 5-6 with 6 M HCl. The crude reaction product is extracted with CH ₂ Cl ₂ (2 × 100 mL), washed with 100 mL of saturated NaCl solution and dried over Na ₂ SO ₄ . After evaporation of the solvent, the black oil obtained is purified by two consecutive chromatography columns (silica gel, eluent: hexane / ethyl acetate (90/10)) and is recrystallized hot in hexane, yielding 1.36 g of pale yellow crystals (8%). ¹ H NMR (CDCl ₃ ): δ = 1.30 ppm (s, 9H, t-Bu), 5.58 (s, 1H, OH), 7.11 (d, J = 2.2Hz, 1H, ArH), 7.26 ( d, J = 2.2 Hz, 1H, ArH), 9.87 (s, 1H, CHO), 10.90 (s, 1H, OH). ¹³ C NMR (63 MHz, CDCl ₃ ): δ = 31.19, 34.25, 119.84, 119.93, 120.56, 143.69, 144.28, 146, 16, 197.06. CnH ₁₄ O ₃ (194): hold. C 68.02, H 7.27; found C 68.18, H 7.16; MS (EI): m / z = 194 (37) [M], 179 (100) [M-CH ₃ ]. Crystals of 1 could be analyzed by X-ray diffraction and the structure was resolved (crystal system: triclinic, space group: P-1). 3,3 '- (3-Oxapentane-1,5-diyldioxy) bis (2-hydroxy-5-tert-butylbenzaldehyde) 2:

To a suspension of NaH (dried beforehand for 1 h under vacuum, 908 mg of a suspension in 60% oil, 22.7 mmol) in 8 ml of dry DSMO under a nitrogen atmosphere, a solution of 1 is added ( 2 g, 10.3 mmol) in 8 ml of dry DSMO for 1 h 30 and with vigorous stirring. The temperature is maintained below 25 ⁰ C using a cold water bath. After stirring for 1 hour, the diethylene glycol ditosylate prepared according to the procedure described in the literature (2.13 g, 5.15 mmol) (ref diethylene glycol ditosylate: JW Comforth et al., Tetrahedron 1973, 29, 1659) is added in one hour. one time. After 48 hours of stirring, the mixture is acidified to pH = 1 with 25 ml of 6 M HCl. The crude reaction product is extracted with CH ₂ Cb (3 × 100 mL), washed with 100 mL of saturated NaCl solution and dried over Na ₂ SO ₄ . After evaporation of the solvent, the oil obtained is dissolved in Et ₂ O (20 mL) and precipitated with 80 mL of hexane (1.2 g, 51%). ¹ H NMR (CDCl ₃ ): δ = 1.29 ppm (s, 18H, t-Bu), 3.98 (m, 4H, OCH ₂ ), 4.27 (m, 4H, OCH ₂ ), 7.17 (d, J = 2.2 Hz, 2H, ArH), 7.25 (d, J = 2.2 Hz, 2H ₁ ArH), 9.90 (s, 2H, CHO) ₁ 10.78 (s, 2H, OH). ¹³ C NMR (63 MHz, CDCl ₃ ): δ = 31.20, 34.0, 69.50, 70.06, 119.83, 120.49, 121.49, 142.92, 146.88, 150.14, 196.46. C ₂₆ H ₃₄ O ₇ (458): hold. (+ H ₂ O) C 65.48, H 7.83; found C 65.53, H 7.61. MS (EI): m / z = 458 (100) [M]. Crystals of 2 could be analyzed by X-ray diffraction and the structure was resolved (crystal system: triclinic, space group: P-1).

Complex Mn '"- Salen 3:

Compound 2 (400 mg, 0.87 mmol) is dissolved in 120 mL of EtOH under a nitrogen atmosphere. To this solution, we add successively (1 S, 2S) - (+) -

1, 2-diaminocyclohexane (100 mg, 0.87 mmol) and manganese (II) diacetate tetrahydrate (214 mg, 0.87 mmol). After stirring overnight, air is bubbled through the solution for 4 hours. The mixture is concentrated to 20 mL, then 20 mL of saturated NaCl solution is added and extracted with 2 x 50 mL of CH ₂ Cl ₂ . The organic phase is then washed with 100 mL of H ₂ O and dried over Na ₂ SO ₄ .

After evaporation of the solvent the product is dried under vacuum and 404 mg is obtained

(74%) of the complex 6 as a microcrystalline black solid. C ₃₂ H ₄₂ N ₂ O ₅ CIMn (625): hold. (+ 2H ₂ O) C 58.14, H 7.01, N 4.24, Cl 5.36, Mn 8.31; found C 57.93, H 7.29, N 4.39, Cl 5.60, Mn 8.14. MS (ES): m / z = 589.2 [M-CP] ⁺ . IR (KBr, errr ¹ ): 1616 (C = N). UV / Vis (CH ₃ OH): λ (ε) = 278 nm (16110 moPW ¹ ), 326 (13110), 414 (5910). [α] _D ²⁰ = 504 deg cm ² g ^"1 (c = 0.048 x ^{10" 3} g / ml, CH ₃ OH).

Example B: Preparation of complex 4

Mn "- Salen 4 complex: Complex 4 is synthesized according to the procedure described above, from 2 (320 mg, 0.70 mmol) in 100 ml of EtOH, (1R, 2R) - (+ -1,2-diaminocyclohexane (75 mg, 0.70 mmol) and Mn (OAc) ₂ -4H ₂ O (171 mg, 0.70 mmol) Yield: 360 mg, 82% as a microcrystalline black solid C ₃₂ H ₄₂ N ₂ O ₅ CIMn (625): Calc (+ H ₂ O) C 59.77, H 6.90, N 4.36, Cl 5.52, Mn 8.55, found C 60.06, H 6.85, N 4.00, Cl 5.40, Mn 8.58. MS (ES): m / z = 589.3 [M-Clf, 1213.6 [Mn ⁺ ₂ Salen ₂ Cr] ⁺ . IR (KBr, cm- ¹ ): 1616 (C = N), UV / Vis (CH ₃ OH): λ (ε) = 278 nm (16,100 MorW ¹ ), 322 (13570), 412 (5500). ] _D ≈ ²⁰ - 496 deg cm ² g ^-1 (c = 0.044 x O 1 ^-3 g / mL, CH ₃ OH).

Example C: Preparation of complex 5

Complex Mn '"- Salen 5:

Complex 5 was obtained as complex 3 from 2 (320 mg, 0.70 mmol) in 100 ml of EtOH, (1S, 2S) - (-) - 1, 2-diphenylethylenediamine.

(148 mg, 0.70 mmol) and Mn (OAc) ₂ -4H ₂ O (171mg, 0.70 mmol). Yield: 450 mg, 89% as a microcrystalline black solid. C ₄₀ H ₄₄ N ₂ O ₅ CIMn (723): hold. (+ 2H ₂ O) C 63.28, H 6.37, N 3.69, Cl 4.68, Mn 7.24; found C 63.35, H 6.26,

N 3.40, Cl 4.78, Mn 7.54. MS (ES): m / z = 687.3 [M-CP] ⁺ . IR (KBr, cm ^-1 ): 1616

(C = N). UVΛ / is (CH ₃ OH): λ (ε) = 276 nm (32500 mol- ¹ cm ^-1 ), 330 (21000), 422

(8360). [α] _D ²⁰ = 433 deg cm ² g ^-1 (c = 0.049 x 10 ^{~ 3} g / m L ₁ CH ₃ OH) Crystals of 5 could be analyzed by X-ray diffraction and the structure was resolved

(crystalline system: triclinic, space group: P-1).

Example D: Preparation of complex 6

Complex Mn ^m -Salen 6:

Complex 6 was obtained as complex 5 (in the same proportions), from (1R2R) - (+) - 1,2-diphenylethylenediamine. Yield: 450 mg, 89% as a microcrystalline black solid. C ₄₀ H ₄₄ N ₂ O ₅ CIMn (723): hold. (+ 2H ₂ O) C 63.28, H 6.37, N 3.69, Cl 4.68, Mn 7.24; found C 63.61, H 6.34, N 3.46, Cl 4.59, Mn 7.01. MS (ES): m / z = 687.3 [M - Clf. IR (KBr, error ¹ ): 1616 (C = N). UVΛ / is (CH ₃ OH): λ (ε) = 276 nm (32600 MorW ¹ ), 328 (22600), 426 (8732). [α] _D ²⁰ = - 443 deg cm ² g ^-1 (c = 0.049 x 10 ^-3 g / mL, CH ₃ OH). Example E Preparation of Complex 8

3,3 '- (3,6-Dioxaoctane-1,8-diyldioxy) bis (2-hydroxy-5-tert-butylbenzaldehyde) 7:

Compound 7 was synthesized using the same procedure as that used to obtain compound 2 from sodium hydride (480 mg of a 60% oil suspension, 11.86 mmol) in 4. dry DSMO ml of 1 (1 g, 5.15 mmol) in 4 mL of dry DSMO and triethylene glycol ditosylate prepared according to the procedure described in the literature (1.18 g, 5.15 mmol) (ref triethylene glycol ditosylate: JW Cornforth et al Tetrahedron 1973, 29, 1659). The reaction crude is dissolved in 10 mL of diethyl ether and precipitated with hexane (100 mL). The resulting oil is recrystallized hot in cyclohexane, resulting in 3 as white crystals (400 mg, 31%). ¹ H NMR (CDCl ₃ ): δ = 1.29 ppm (s, 18H, t-Bu), 3.77 (s, 4H, OCH ₂ ), 3.89 (m, 4H, OCH ₂ ), 4.29 (m, 4H). , OCH ₂ ), 7.17 (d, J = 2.2 Hz, 2H, ArH), 7.24 (d, J = 2.2 Hz, 2H, ArH), 9.92 (s, 2H, CHO), 10.69 (s, 2H). , OH). ¹³ C NMR (63 MHz, CDCl ₃ ): δ = 31.16, 34.25, 69.10, 69.28, 70.66, 119.19, 119.86, 120.90, 142.66, 146.82, 149.98, 196.03. C ₂₈ H ₃₈ O ₈ (502): hold. C 66.85, H 7.56; found C 66.52, H 7.14. MS (DCI / NH ₃ ): m / z = 520 (100) [M + NH ₄ ⁺ ]. Crystals of 7 could be analyzed by X-ray diffraction and the structure was resolved (crystalline system: monoclinic, space group: C2 / c).

Mn ^m -Salen 8 complex: The complex 8 is synthesized according to the procedure described above, from 7 (400 mg, 0.80 mmol) in 80 mL of EtOH, (1S, 2S) - ( ⁺ ) -1.2 -diaminocyclohexane (91 mg, 0.80 mmol) and Mn (OAc) ₂ -4H ₂ O (195 mg, 0.70 mmol). Yield: 365mg, 69% as a microcrystalline black solid. C ₃₄ H ₄₆ N ₂ O ₆ CIMn (669): hold. (+ CH ₂ Cl ₂ ) C 55.70, H 6.37, N 3.71, Cl 4.70, Mn 7.29; found C 55.65, H 6.56, N 3.65, Cl 4.68, Mn 7.49. MS (ES): mfz = 633.4 [M-Gif, 656.4 [Mn ⁺ Sal] ^{+ +} ) ⁺ , 672.2 [Mn + ( ⁺ ) ⁺ K ⁺ ] ⁺ . IR (KBr, error ¹ ): 1621 (C = N). UVΛ / is (CH ₃ OH): λ (ε) = 274 nm (10770 MorW), 324 (8983), 412 (3760). [α] _D ²⁰ = 262 deg cm ² g ^-1 (c = 0.049 x 10 ^-3 g / m L ₁ CH ₃ OH).

Example F: Preparation of complex 11

Benzenedimethanol di-p-tosylate 9

In a solution of 3 g NaOH (75.2 mmol) in 15 mL H ₂ O, 4 g (29 mmol) of 1,3-benzenedimethanol are dissolved. Then, a solution of tosyl chloride (12.16 g, 63.9 mmol) in 25 mL THF is added dropwise over a period of 20 minutes. After stirring overnight, the mixture is extracted with 100 mL of toluene, washed with 100 mL of H ₂ O, 100 mL of saturated NaHCO ₃ solution and dried over Na ₂ SO ₄ . The reaction crude is then dissolved in 10 ml of CH ₂ Cb and precipitated with hexane (100 ml). The white precipitate is filtered and then dried under vacuum (4.5 g, 35%). ¹ H NMR (CDCl ₃ ): δ = 2.44 ppm (s, 3 H ₁ CH ₃ ), 4.98 (s, 4H, CH ₂ ), 7.09 (s, 1H, ArH), 7.18-7.28 (m, 3H). , ArH), 7.30 (d, J = 8.7 Hz, 4H, HTS), 7.77 (d, J = 8.4 Hz, 4H, TsH). C ₂₂ H ₂₂ O ₆ S ₂ (446): hold. (+ 0.5 H ₂ O) C 58.02, H 5.27; found C 58.41, H 5.02. MS (ES): m / z = 469 [M + Na ⁺ ]. 3,3 '- (1,3-Benzenediyldioxy) bis (2-hydroxy-5-tert-butylbenzaldehyde) 10:

Compound 5 was synthesized according to the same procedure as that used to obtain compound 2, from sodium hydride (440 mg of a 60% oil suspension, 10.67 mmol) in 6 ml dry DSMO. of 1 (900 mg, 4.64 mmol) in 6 ml of dry DSMO and 9 (1.04 g, 2.32 mmol). The reaction is monitored with ¹ H NMR, showing that there remains 2,3-dihydroxy-5-fe-butylbenzaldehyde in solution. Compound 9 is then added in two portions (100 mg, 2.2 mmol) at t = 12 and 24 h. The crude reaction product is purified by chromatography (silica gel, eluent: hexane / ethyl acetate (90/10)) and then recrystallized under heat in cyclohexane, yielding 151 mg as a white solid (13%). ¹ H NMR (CDCl ₃ ): δ = 1.24 ppm (s, 18H, t-Bu), 5.18 (s, 4H, CH ₂ ), 7.15 (d, J = 2.1 Hz, 2H, ArH), 7.19 ( d, J = 2.1 Hz, 2H, ArH), 7.39 (m, 3H, ArH), 7.57 (s, 1H, ArH), 9.89 (s, 2H, CHO), 10.93 (s, 2H, OH ). ¹³ C NMR (63 MHz, CDCl ₃ ): δ = 31.16, 34.20, 71.54, 120.06, 120.43, 121.65, 126.8O ₁ 127.35, 128.88, 137.18, 142.72, 146.54, 150.26, 196.84. C ₃₀ H ₃₄ O ₆ (490): hold. (+ 0.1 H ₂ O) C 73.18, H 6.89; found C 72.97, H 6.51. MS (ES): m / z = 491.1 [M + H ⁺ ], 513.3 [M + Na ⁺ ], 529.3 [M + K ⁺ ].

Complex Mn '"- Salen 11:

Complex 11 is synthesized according to the procedure described above, starting from 5 (65 mg, 0.13 mmol) in 20 mL of EtOH, (1S, 2S) -

(+) - 1,2-diaminocyclohexane (15 mg, 0.13 mmol) and Mn (OAc) ₂ -4H ₂ O (33 mg, 0.13 mmol). Yield: 40 mg, 47% as a brown powder. C ₃₆ H ₄₂ N ₂ O ₄ CIMn (657): hold. C 65.80, H 6.44, N 4.26, Cl 4.50, Mn 8.36; found C 65.75, H 6.49, N 3.96, Cl 4.21, Mn 8.56. MS (ES): m / z = 621.4 [M-CI ^{"] +,} 679.6 [Mn" Salen + Na ^{+] +.} IR (KBr, cm ^'1 ): 1615 (C = N). UV / Vis (CH ₃ OH): λ (ε) = 276 nm (11370 MorW ¹ ), 318 (8763), 408 (3653). [α] _D ²⁰ = 203 deg cm ² g ^-1 (c = 0.049 x 10- ³ g / mL, CH ₃ OH). Example G Preparation of Complex 18

2,6-Dibromo-4-tert-butylphenol 12 (ref for the preparation of 2,6-dibromo-4-fe / Y-butylphenol: KS Chang et al., J. Org Chem, 1996, 61, 8414-8 8418): To a solution of 4-Fe / f-butylphenol (5 g, 0.033 mol) and sodium acetate (10 g, 0.121 mol) in glacial acetic acid (140 mL) was added dropwise. drop a solution of bromine (3.42 mL, 0.066 mol) in acetic acid (60 mL) for 0.5 h, then the mixture is stirred for 12 h. The solvent is evaporated, then water is added to the residue and extracted with dichloromethane. The organic phase is then washed with a saturated solution of Na ₂ S ₂ O ₅ then NaHCO ₃ and dried (MgSO ₄ ). The solvent is evaporated. A colorless oil (9.1 g, 90%) is obtained. ¹ H NMR (CDCl ₃ ): δ = 1.30 ppm (s, 9H, t-Bu), 5.7 (s, 1H, OH), 7.4 (s, 2H, ArH).

Compound 13:

To a solution of 12 (3.82 g, 0.0124 mol) in 30 mL of CH ₂ Cl ₂ / H ₂ O (10/7 v / v), a large excess of allyl bromide is added at room temperature. 8.52 ml of a 40% by weight solution of / 7Bu ₄ NOH in water are then added, the mixture is then placed under vigorous stirring for 24 hours. The addition of 200 mL of 1M NaOH is followed by extraction with CH ₂ Cl ₂ (3 x 100 mL). The organic phases are combined and washed with 1M NaOH solutions (100 ml) and water (2 x 200 ml), dried (MgSO ₄ ), filtered and concentrated. The crude reaction product is dissolved in CH ₂ Cl ₂ and the ammonium salt is precipitated by addition of ethyl ether. After filtration, the filtrate is dried under vacuum; a colorless oil (4.1 g, 95%) is then obtained. ¹ H NMR (CDCl ₃ ): δ = 1.3 ppm (s, 9H, t-Bu),

4.5 (m, 2H), 5.4-5.5 (m, 2H), 6.3 (m, 1H), 7.5 (s, 2H, ArH). ¹³ C NMR (63 MHz, CDCl ₃ ): δ = 31.2, 34.6, 73.9, 118.5, 133.2. C ₁₃ H ₁₆ O ₁ Br ₂ (348): hold. C 44.86, H

4.63; found C 44.57, H 4.55. MS (EI): m / z = 348 [M] _1333, 307, 267, 226, 147,

132, 91, 77, 57, 41.

Compound 14: To a solution of 13 (6.05 g, 0.017 mol) in anhydrous diethyl ether (20 mL), under an inert atmosphere, a solution of β-BuLi in a solution of 1 7-BuLi is added dropwise at -78 ^° C. hexane (1.6 M, 13 mL, 0.0204 mol). After 1 hour of agitation at this temperature, a yellow solution is obtained to which is added dropwise and at -78 ⁰ C a solution of acetone (1.65mL, 0.0221 mol) in anhydrous ether (10 mL) (still under an inert atmosphere). The mixture is then allowed to come to room temperature and stirred for an additional hour. Water is then added at 5 ° C. The mixture is extracted with ether (3 x 100 mL). The organic phases are combined, washed with water (2 × 100 mL) and dried over MgSO ₄ . The solvent is evaporated and the crude reaction product is purified by chromatography column using hexane / ethyl acetate (9/1) as eluent, a colorless oil (3.7 g, 65%) is then obtained. ¹ H NMR (CDCl ₃ ): δ = 1.3 ppm (s, 9H, t-Bu), 1.6 (s, 6H, CH ₃ ), 3.8 (s, 1H, OH), 4.5 (m, 2H) , 5.4-5.5 (m, 2H), 6.3 (m, 1H), 7.32 (d, J = 2.3Hz, 1H,) 7.44 (d, J = 2.3Hz, 1H,). ¹³ C NMR (63 MHz, CDCl ₃ ): δ = 31.22, 34.25, 73.19, 74.34, 117.24, 118.27, 122.93, 129.75, 132.95, 142.15, 148.17, 150.85. Ci ₆ H ₂₃ O ₂ Br ₁ (328): hold. C 58.72, H 7.08; found C 58.49, H 7.09. MS (EI): m / z = 328 [M] _1311, 270, 255, 91, 77, 43.

Compound 15:

The NaH (0.78 g of a 60% suspension in oil, 20.34 mmol) is washed with pentane (3 × 4 mL), then, under nitrogen, a solution of 14 (3.7 g, 11.3 mmol) in THF (15 mL). The mixture is stirred for 3 hours at room temperature. Then, a solution of diethylene glycol ditosylate (2.8 g, 6.9 mmol) in anhydrous DMF (10 mL) is added all at once. After stirring for 48 h, a saturated solution of NaCl is added (100 mL) and then extracted with CH ₂ Cl ₂ (3 x 100 mL). The organic phases are combined, washed with water (2 x 100 mL), dried, filtered and concentrated. The reaction crude is purified by chromatography using hexane / ethyl acetate (96/4) as eluent. A colorless oil (2.3 g, 55%) is obtained. ¹ H NMR (CDCl ₃ ): δ = 1.26 ppm (s, 18H, t-Bu), 1.62 (s, 6H, CH ₃ ), 3.43 (t, J = 5.5 Hz, 4H, CH ₂ ), 3.66 ( t, J = 5.5 hz, 4H, CH ₂ ), 4.48 (m, 4H), 5.24-5.48 (m, 4H), 6.10 (m, 2H), 7.43 (d, J = 2.9 Hz, 2H, ArH) 7.48 (d, J = 2.9 Hz, 2H, ArH). ¹³ C NMR (63 MHz, CDCl3): δ = 28.27, 31.31, 62.14, 71.00, 73.82, 77.51, 117.37, 118.27, 124.69, 129.73, 133.61, 139.71, 147.85, 151.29. C ₃₆ H ₅₂ O ₅ Br ₂ (724.6): hold. C 59.67, H 7.23; found C 59.42, H 7.30. MS (DCI / NH ₃ ): m / z δ 742 [M + NH ₄ ⁺ ]

Compound 16: To a solution of 15 (1.6 g, 2.2 mmol) and TMEDA (330 mg, 2.9 mmol) in anhydrous ether (5 ml) at -80 ^° C., dropwise and under an inert atmosphere are added dropwise. n-BuLi (1.6 M, 4 mL, 6.4 mmol). The yellow solution obtained is stirred at -90 ^° C. for 1 h. Then, a solution of anhydrous DMF (1.8 ml, 22.4 mmol) in ether (2 ml) is added at -78 ^° C., still under an inert atmosphere. Then the mixture is allowed to come to room temperature and stirred for a further hour. Water is added at 5 ^° C. The mixture is extracted with ether (3 x 100 mL), the organic phases are combined and washed with water (2 x 100 mL) and dried over MgSO ₄ . The solvent is evaporated and the crude reaction product is purified by chromatography column using hexane / ethyl acetate (9/1) as eluent. A pale yellow oil (530 mg, 40%) is then obtained. ¹ H NMR (CDCl ₃ ): δ = 1.29 ppm (s, 18H, t-Bu), 1.65 (s, 12H, CH ₃ ), 3.45 (t, J = 5.6 Hz, 4H, CH ₂ ), 3.68 (t, J = 5.6 Hz ₁ H 4, CH _2), 4.46 (m, 4H), 5.30- 5.40 (m, 4H), 6.05 (m, 1H), 7.75 (d, J = 2.8 Hz , 2H, 7.83 (d, J = 2.8 Hz, 2H), 10.28 (s, 2H). ¹³ C NMR (63 MHz, CDCl ₃ ): δ = 28.14, 31.25, 34.66, 62.11, 70.78, 71.03, 78.94, 117.73, 124.98, 129.70, 131.88, 132.79, 139.15, 142.43, 149.2, 190.64. C ₃₈ H ₅₄ O ₇ (622.85): hold. (+ H ₂ O) C 71.62, H 8.80; found C 71.56, H 9.21. MS (ES) m / z = 546 [M + Na ⁺ ].

Compound 17: To a solution of 16 (120 mg 0.193 mmol) in MeOH (3 mL) was added, under an inert atmosphere, catalytic amounts of Pd (PPh ₃ ) ₄ (11.1 mg, 0.0098 mmol). Then stirred 5 min. and K ₂ CO ₃ (160 mg, 1.16 mmol) is added. The reaction is monitored by TLC. After stirring for 2 hours, it is finished. The crude reaction is concentrated; then water (20 mL) is added. The aqueous phase is extracted with CH ₂ Cl ₂ (3 x 20 mL) and dried over Na ₂ SO ₄ . The organic phase is concentrated and purified by chromatography using CH ₂ Cl ₂ as eluent to give a pale yellow oil (90 mg, 86%). ¹ H NMR (CDCl ₃ ): δ = 1.29 ppm (s, 18H, t-Bu), 1.64 (s, 12 H, CH ₃ ), 3.54 (t, J = 5.0 Hz, 4H, CH ₂ ), 3.73 (t, J = 5.0 Hz, 4H, CH ₂ ), 7.49 (d, J = 2.4 Hz , 2H ₁ ), 7.65 (d, J = 2.4 Hz, 2H), 10.06 (s, 2H), 10.66 (s, 2H). ¹³ C NMR (63 MHz, CDCl ₃ ): δ = 26.55, 31.28, 34.52, 62.11, 70.75, 77.95, 121.50, 127.13, 128.42, 131.79, 142.06, 157.50, 194.80. C ₃₂ H ₄₆ O ₇ (542): hold. C 70.82, H 8.54; found C 70.46, H 8.62. MS (ES) m / z = 565.25 [M + Na ⁺ ].

Complex Mn '"- Salen 18:

Compound 17 (80 mg, 0.1475 mmol) is dissolved under an inert atmosphere in 50 ml of EtOH. Then, (1f?, 2R) - (+) - 1, 2-diaminocyclohexane (17 mg, 0.1475 mmol), manganese (II) diacetate tetrahydrate (36.35 mg, 0.1475 mmol) are added successively. After stirring overnight, air is bubbled through the solution for 4 hours. The mixture was concentrated to 20 mL, then 20 mL of saturated NaCl solution was added and extracted with 2x50 mL of CH ₂ Cl ₂ . The organic phase is then washed with 100 mL of H ₂ O and dried over Na ₂ SO ₄ . After evaporation of the solvent, the product is dried under vacuum and 85 mg (82%) of the complex 18 is obtained in the form of a microcrystalline black solid. C ₃₈ H ₅₄ N ₂ O ₅ CIMn (709): hold. C 64.35, H 7.67, N 3.95, Mn 7.75, Cl 5.00; found C 64.66, H 7.61, N 3.54, Mn 7.75, Cl 5.39. MS (ES): m / z = 673.55 [M-Cr] ⁺ , IR (KBr, error ¹ ): 1631 (C = N). UVΛ / is (CH ₃ OH): λ (ε) = 274 nm (14000 L morW ¹ ), 290 (13210), 318 (8928), 354 (5714), 416 (4103). [α] _D ²⁰ = -231 deg cm ² g ^"1 (c = 0.039 x ^{10" 3} g / ml, CH ₃ OH).

Example H Preparation of Complex 21

Compound 19:

To a suspension of NaH (0.22 g of a suspension in 60% oil, 5.5 mmol) in THF (5 mL), under nitrogen, a solution of 14 (1.2 g, 3.7 mmol) in THF (5 ml). The mixture is stirred for 3 hours at room temperature. Then, a solution of triethylene glycol ditosylate (0.924 g, 2.0 mmol) in anhydrous DMF (5 ml) was added all at once. After stirring for 48 h, a saturated solution of NaCl is added (100 ml) and then extracted with CH ₂ Cb (3 x 100 ml), the organic phases are combined and washed with water (2 ml). x 100 ml), dried, filtered and concentrated. The crude reaction product is purified by chromatography using hexane / ethyl acetate (9/1) as eluent. A colorless oil (0.85 g, 55%) is obtained. ¹ H NMR (CDCl ₃ ): δ = 1.27 ppm (s, 18H, t-Bu), 1.62 (s, 12H, CH ₃ ), 3.43 (t, J = 5.4 Hz, 4H, CH ₂ ), 3.64 (t, J = 5.4 Hz, 4H, CH ₂ ), 3.65 (s, 4H) 4.46 (m, 2H), 5.45 (m, 4H), 5.30- 5.40 (m, 4H), 6.05 (m). , 2H), 7.75 (d, J = 2.8 Hz, 2H,) 7.83 (d, J = 2.8 Hz, 1H,). ¹³ C NMR (63 MHz, CDCl ₃ ): δ = 28.27, 31.31, 34.66, 62.14, 70.66, 70.94, 73.82, 77.36, 117.33, 118.27, 124.69, 129.73, 133.64, 139.75, 147.82, 151.33. C ₃₈ H ₅₆ O ₆ Br ₂ (768.7): hold. C 59.38, H 7.34; found C 59.51, H 7.52. MS (DCI / NH ₃ ) m / z = 786 [M + NH ₄ ⁺ ].

Compound 20:

To a solution of 19 (0.7 g, 0.93 mmol) and TMEDA (140 mg, 1.22 mmol) in anhydrous ether (3 mL) at -90 ^° C., n-BuLi is added dropwise and under an inert atmosphere. (1.6 M, 1.5 mL, 2.4 mmol). The yellow solution obtained is stirred at -90 ^° C. for 1 h. Then a solution of anhydrous DMF (0.8 mL, 10.3 mmol) in ether (1 mL) is added at -78 ^° C., still under an inert atmosphere. Then, the mixture is allowed to return to room temperature and stirring is continued for another hour. Then, at 5 ° C, water is added. The mixture is extracted with CH ₂ Cl ₂ (3 x 50 mL), the organic phases are combined and washed with water (2 x 50 mL) and dried over MgSO ₄ . The solvent is evaporated and the crude reaction product is purified by chromatography column using hexane / ethyl acetate (9/1) as eluent. A pale yellow oil (230 mg) is then obtained which is a difficultly separable mixture of protected and deprotected products. This mixture (230 mg) is dissolved in MeOH (5 mL); Catalytic amounts of Pd (PPh ₃ ) ₄ (16 mg, 0.014 mmol) are added under an inert atmosphere. Then, stirring 5 min. and we add K 2 CO ₃ (230 mg, 1.66 mmol). The reaction is monitored by TLC. After stirring for 2 hours, it is finished. The crude reaction is concentrated; then water (20 mL) is added. The aqueous phase is extracted with CH ₂ Cl ₂ (3 x 20 mL) and dried over Na ₂ SO ₄ . The organic phase is concentrated and purified by chromatography using CH ₂ Cl ₂ as eluent. A pale yellow oil (160 mg, 30%) is obtained. ¹ H NMR (CDCl ₃ ): δ = 1.30 ppm (s, 18H, t-Bu), 1.63 (s, 12H, CH ₃ ), 3.51 (t, J = 4.8 Hz, 4H, CH ₂ ), 3.70 (t, J = 4.8 Hz, 4H, CH ₂ ), 3.72 (s, 4H), 7.49 (d, J = 2.3 Hz, 2H), 7.65 (d, J = 2.3 Hz ₁ 2H, ), 10.09 (s, 2H), 10.61 (s, 2H). ¹³ C NMR (63 MHz, CDCl ₃ ): δ = 26.55, 31.28, 34.07, 62.14, 70.68, 77.92, 121.56, 125.85, 131.78, 132.32, 142.06, 157.50, 194.70. C ₃₄ H ₅₀ O ₈ (586): hold. (+0.4 CH ₂ Cl ₂ ) C 66.56, H 8.25; found C 66.98, H 7.81. MS (DCI ₃ NH ₃ ) m / z = 604 [M + NH ₄ ⁺ ].

Complex Mn "- Salen 21:

Complex 21 is synthesized according to the procedure described above, from a solution of (88.0 mg, 0.15 mmol) in 50 mL of EtOH, (1S, 2S) - (+) - 1, 2-diaminocyclohexane (17.1 mg, 0.15 mmol) and

Mn (OAc) ₂ · 4H ₂ O (36.76 mg, 0.15 mmol). Yield: 90 mg, 80% as a microcrystalline solid. C ₄₀ H ₅₈ N ₂ O ₆ CIMn (753.3): hold. (+0.4 CH ₂ Cl ₂ ) C 63.78, H 7.76, N 3.72, Mn 6.98, Cl 4.51; found C 63.55, H 7.56, N 3.65, Mn 6.61, Cl 4.78. MS (ES): m / z = 717.5 [M-Clf. Ir (KBr, cm ^"1): 1615 (C = N) UVΛ / is (CH ₃ OH.): Λ (ε) = 290nm (19031 mol ^{'W 1),} 318 (13379), 356 (8469), 412 (6124). [α] _D ²⁰ = + 481.5 deg cm ² g ^'1 (c = 0.108 x 10 ^"3 g / ml, CH ₃ OH).

Example I: Preparation of complex 22

Complex Mn '"- Salen 22:

Complex 22 is synthesized according to the procedure described above, from a solution of 20 (47 mg, 0.08 mmol) in 20 mL of EtOH, (1R, 2R) - (-) - 1, 2-diphenylethylenediamine. (17 mg, 0.08 mmol) and

Mn (OAc) ₂ · 4H ₂ O (19.6 mg, 0.08 mmol). Yield: 85 mg, 67% as a brown solid. C ₄₈ H ₆₀ N ₂ O ₆ CIMn (851.4): hold. C 67.72, H 7.10, N 3.29, Mn 6.46, Cl 4.16; found C 67.96, H 7.29, N 2.94, Mn 6.21, Cl 4.67. MS (ES): m / z = 815.5 [M-Cr] ⁺ . IR (KBr, cnT ¹ ): 1612 (C = N). UV / Vis (CH ₃ OH): λ (ε) = 274 nm (16440 mol ^{"1cm" 1),} 290 (14126), 326 (10210), 356 (6625) 424 (4352). [α] _D ²⁰ = - 237 deg cm ² g ^"1 (c = 0.038 x 1 Q- ³ g / mL, CH ₃ OH).

Example J: Preparation of Complex 27:

Compound 24:

To a suspension of NaH (0.60 g of a suspension in 60% oil, 15.0 mmol) in THF (5 mL), under nitrogen, a solution of 14 (2.8 g, 8.54 mmol) is added dropwise. in THF (5 mL). The mixture is stirred for 3 hours at room temperature. Then, a solution of aromatic ditosylate 23 (2.0 g, 3.98 mmol) in anhydrous DMF (5 mL) was added in one go. Compound 23 was prepared according to the literature: JS Bradshaw et al., Supramolecular Chem., 1993, 1, 267-273). After stirring for 48 hours, 100 saturated NaCl solution, then extracted with CH ₂ Cl ₂ (3 x 100 mL); the organic phases are combined, washed with water (2 x 100 mL), dried, filtered and concentrated. The reaction crude is purified by chromatography using the hexane / ethyl acetate system (95/5) as eluent. A colorless oil (1.45 g, 42%) is obtained. ¹ H NMR (CDCl ₃ ): δ = 1.22 ppm (s, 18H, t-Bu), 1.70 (s, 12H, CH ₃ ), 4.31 (s, 4H), 4.48 (m, 4H), 4.52 (m, 2H), 5.23- 5.47 (m, 6H), 6.08 (m, 3H), 6.86 (s, 2H), 6.89 (s, 1H), 7.45 (d, J = 2.3 Hz ₁ 2H) 7.52 (d, J = 2.3 Hz, 1H). ¹³ C NMR (63 MHz, CDCl ₃ ): δ = 28.32, 31.23, 34.20, 64.54, 73.66, 77.36, 112.31, 117.23, 118.78, 118.91, 124.33, 129.75, 133.20, 133.33, 139.87, 141.05, 151.34, 158.76. C ₄₃ H ₅₆ O ₅ Br ₂ (812.7): hold. C 63.55, H 6.95; found C 63.21, H 6.83. MS (DCI / NH ₃ ) m / z = 830 [M + NH ₄ ⁺ ].

Compound 25:

To a solution of 24 (0.32 g, 0.39 mmol) and TMEDA (66 mg, 0.6 mmol) in anhydrous ether (5 mL) at -80 ^° C., n-BuLi is added dropwise and under an inert atmosphere. (1.6 M, 0.75 mL, 1.2 mmol). The yellow solution obtained is stirred at -90 ^° C. for 1 h. Then a solution of anhydrous DMF (0.25 mL, 3.25 mmol) in ether (0.25 mL) is added at -78 ^° C., still under an inert atmosphere. The mixture is then allowed to come to room temperature and stirred for another hour. Then, at 5 ° C, water is added. The mixture is extracted with CH ₂ Cl ₂ (3 x 100 mL), the organic phases are combined and washed with water (2 x 100 mL) and dried over MgSO ₄ . After the solvent has evaporated, the compound (280 mg, 98%) is obtained as a pale yellow oil. ¹ H NMR (CDCl ₃ ): δ = 1.29 ppm (s, 18H, t-Bu), 1.74 (s, 12H, CH ₃ ), 4.35 (s, 4H), 4.44 (m, 4H), 4.53 (m, 2H), 5.23-5.48 (m, 6H), 6.05 (m, 3H), 6.87 (s, 2H), 6.91 (s, 1H,) 7.77 (d, J = 2.4 Hz, 2H) 7.86 (d, J = 2.4 Hz, 2H), 10.29 (s, 2H). ¹³ C NMR (63 MHz, CDCl ₃ ): δ = 28.37, 31.25, 34.66, 64.73, 68.75, 78.98, 112.26, 117.52, 117.74, 118.16, 125.16, 129.76, 131.79, 132.73, 133.30, 138.90, 140.69, 147.03, 190.67. . C ₄₅ H ₅₈ O ₇ (711): hold. (+ 0.4 CH ₂ Cl ₂ ) C 73.23, H 7.96; found C 73.25, H 7.88 MS (DCI / NH ₃ ) m / z = 728 [M + NH ₄ ⁺ ]. Compound 26:

To a solution of 25 (280 mg, 0.385 mmol) in MeOH (6 mL), catalytic amounts of Pd (PPh ₃ ) ₄ (20.0 mg, 0.019 mmol) are added under an inert atmosphere. Then stirred 5 min. and K 2 CO ₃ was added (360 mg, 2.61 mmol). The reaction is monitored by TLC. After stirring for 2 hours, it is finished. The reaction crude is concentrated, then water (20 ml) is added. The aqueous phase is extracted with CH ₂ Cl ₂ (3 × 40 mL) and dried over Na ₂ SO ₄ . The organic phase is concentrated and purified by chromatography using hexane / ethyl acetate (9/1) as eluent. Compound 26 is obtained as a pale yellow oil (145 mg, 64%). ¹ H NMR (CDCl ₃ ): δ = 1.26 ppm (s, 18H, t-Bu), 1.72 (s, 12H, CH ₃ ), 3.95 (s, 4H, CH ₂ ), 4.8 (s, 1 H, OH), 6.83 (s, 2H), 6.93 (s, 1H), 7.48 (d, J = 2.7 Hz, 2H), 7.72 (d, J = 2.7 Hz, 2H) 10.01 (s, 2 H), 11.01 (s, 2H). ¹³ C NMR (63 MHz, CDCl ₃ ): δ = 26.80, 31.25, 34.22, 64.74, 78.30, 113.26, 118.14, 121.15, 127.97, 132.07, 132.42, 140.65, 142.19, 156.08, 157.53, 195.62. C ₃₆ H ₄₆ O ₇ (590.76): hold. (+ 0.7 CH ₂ Cl ₂ ) C 67.79, H 7.35; found C 67.90, H 7.26. MS (DCI / NH ₃ ) m / z = 608 [M + NH ₄ ⁺ ].

Complex Mn ^ -Salen 27:

Complex 27 is synthesized according to the procedure described above, from a solution of 26 (130 mg, 0.22 mmol) in 50 mL of EtOH, (1S, 2S) - (+) - 1, 2- diaminocyclohexane (25 mg, 0.22 mmol) and

Mn (OAc) ₂ · 4H ₂ O (53.9 mg, 0.22 mmol). Yield: 120 mg, 73% as a microcrystalline solid. C ₄₂ H ₅₄ N ₂ O ₅ CIMn (757.3): hold. (+ 0.6 CH ₂ Cl ₂ ) C 63.38, H 6.77, N 3.47, Mn 6.81, Cl 4.39; found C 63.01, H 6.7, N 3.35, Mn 6.89, Cl 4.77. MS (ES): m / z = 721.8 [M-Cr] ⁺ . IR (KBr, cm- ¹ ): 1615 (C = N), UV / Vis (CH ₃ OH): λ (ε) = 278 nm (14663 mol- ¹ cm- ¹ ), 320 (8333), 358 (5292); ), 412 (3805) [α] _D ²⁰ = + 275 deg cm ² g ^-1 (c = 0.052 x 10 ³ g / mL, CH ₃ OH). Example K: Preparation of Complex 32:

Compound 28:

To a solution of 14 (2.00 g, 5.75 mmol) in anhydrous Et ₂ O (8 mL) under nitrogen at -78 ° C is added n-BuLi (1.6 M, 4.31 mL, 6.89 mmol) dropwise. After stirring for 1 hour at -78 ^° C., 4,4'-difluorobenzophenone (2.51 g, 11.5 mmol) in anhydrous I ¹ Et ₂ O (30 ml) is added dropwise at -78 ° C. nitrogen. The solution is allowed to rise to ambient temperature and with stirring for an additional hour. Water is slowly added to the solution at 5 ^° C. The reaction medium is extracted with I ¹ and ₂ O (3 × 100 ml), the combined organic phases are washed with I ¹ H ₂ O (2 × 100 ml) ) and dried over MgSO ₄ . The solvent is evaporated and the crude is redissolved in a minimum of CH ₂ Cl ₂ , hexane is added and the mixture is placed at -20 ⁰ C for the night. The supernatant is collected by filtration and the solvent evaporated to give a pale yellow solid (2.51 g, 90%). ¹ H NMR (CDCl ₃ ): δ = 1.11 ppm (s, 9H, t-Bu), 3.8 (m, 2H, OH), 5.02-5.14 (m, 2H), 5.64-5.73 (m, 2 H), 5.71 (s, 1H, OH), 6.49 (d, J = 2.5 Hz, 1H), 7.02 (m, 4H), 7.24 (m, 4H), 7.48 (d, J = 2.5 Hz). , 1H,). ¹³ C NMR (63 MHz, CDCl ₃ ): δ = 31.00, 34.41, 73.70, 81.83, 114.54, 114.89, 117.39, 118.71, 126.97, 129.60, 129.74, 130.41, 132.32, 141.81, 151.35, 160.18, 164.09. C ₂₆ H ₂₅ O ₂ Br ₁ F ₂ (487): hold. C 64.07, H 5.17; found C 64.24, H 4.71. MS (ES): m / z = 510 [M + Na ⁺ ]. Compound 29:

To a slurry of NaH with stirring (0.24 g, 6.2 mmol, 60% dispersed in oil) in anhydrous THF (6 mL) is added dropwise a solution of 28 (2.0 g, 4.1 mmol) in water. THF (8 mL) under nitrogen. The reaction medium is stirred for 3 h at room temperature. To the resulting suspension, a solution of diethylene glycol ditosylate (0.85 g, 2.05 mmol) in anhydrous DMF (8 mL) was added all at once and the resulting mixture was stirred for 48 h. The reaction is trapped by the addition of saturated aqueous NaCl (100 mL) and extracted with CH ₂ Cl ₂ (3 x 100 mL), filtered and concentrated. The residue is purified by chromatography on silica with a hexane / ethyl acetate (95/5) eluent mixture to obtain a pale yellow solid (0.643 g, 30%). ¹ H NMR (CDCl ₃ ): δ = 1.24 ppm (s, 18H, t-Bu), 3.10 (t, J = 4.9 Hz, 4H, CH ₂ ), 3.70 (t, J = 4.9 Hz, 4H, CH ₂ ), 3.92 (m, 4H), 4.88-4.99 (m, 4H), 5.47-5.62 (m, 2H), 6.92 (m, 8H) ₁ 7.42 (m, 8H), 7.50 ( d, J ≈ 2.5 Hz, 2H, ArH), 7.70 (d, J = 2.5 Hz, 2H). ¹³ C NMR (63 MHz, CDCl ₃ ): δ = 31.24, 34.56, 63.39, 70.76, 72.29, 84.92, 114.39, 114.71, 116.74, 118.12, 126.22, 129.73, 129.86, 130.76, 133.30, 137.77, 138.87, 147.26, 159.66 , 163.57. C ₅₆ H ₅₆ O ₅ Br ₂ F ₄ (1044.87): hold. (+ 0.4 CH ₂ Cl ₂ ) C 62.79, H 5.31; found C 62.98, H 5.30. MS (ES): m / z = 1068 [M + Na ⁺ ].

Compound 30:

To a well stirred solution of 29 (0.410 g, 0.39 mmol) and TMEDA (0.1 mL) in I ¹ Et ₂ O anhydrous (2.5 mL) at -78 ° C was added n-BuLi (1.6 M, 1.0 mL, 1.2 mmol) dropwise under nitrogen. The yellow solution is stirred at -78 ^° C. for 1 h. A solution of anhydrous DMF (0.5 mL, 3.2 mmol) in ¹ I and ₂ O (2 mL) is added at -78 ^° C. under nitrogen. The solution is allowed to rise to ambient temperature and with stirring for an additional hour. I ¹ H ₂ O is slowly added at 5 ⁰ C. The reaction medium is extracted with CH ₂ Cl ₂ (3 x 30 mL), the combined organic phases are washed with I ¹ H ₂ O (2 x 30 mL) ) and dried over MgSO ₄ . The solvent is evaporated, the crude obtained is dissolved in an ethyl acetate / hexane mixture (30 ml / 30 ml) and placed at -20 ^° C. for the night. The solid is collected and dried under vacuum (338 mg, 92%). ¹ H NMR (CDCl ₃ ): δ = 1.28 ppm (s, 18H, t-Bu), 3.13 (t, J = 5.1 Hz, 4H, CH ₂ ), 3.71 (t, J - 5.1 Hz, 4H). , CH ₂ ), 3.89 (d, J = 5.2 Hz, 4 H) ₁ 4.92-5.04 (m, 4H), 5.49 (m, 2H), 6.94 (m, 8H), 7.44 (m, 8H), 7.81 (d, J = 2.9 Hz, 2H), 8.08 (d, J = 2.9 Hz, 2H ₁ ) 10.12 (s, 2H). ¹³ C NMR (63 MHz, CDCl ₃ ): δ = 31.18, 34.72, 63.33, 70.75, 77.20, 84.21, 114.48 114.80, 117.11, 125.69, 129.82, 129.95, 132.48, 132.86, 137.02, 138.52, 158.21, 159.75, 163.66, 190.26. C ₅₈ H ₅₈ O ₇ F ₄ (942): hold. (+ 0.2 CH ₂ Cl ₂ ) C 72.81, H 6.13; found C 72.90, H 5.88. MS (ES) m / z = 965.5 [M + Na ⁺ ], 981 [M + K ⁺ ], 997.5 [M + MeOH + Na ⁺ ], 1013.5 [M + MeOH + K ⁺ ].

Compound 31: To a solution of 30 (220 mg 0.234 mmol) in MeOH (5 mL) were added catalytic amounts of Pd (PPHs) ₄ (12.5 mg, 0; 011 mmol) under nitrogen. The yellow solution is stirred for 5 min, and K ₂ CO ₃ (200 mg, 1.45 mmol) is added. The reaction is monitored by TLC and is complete in one hour. The reaction medium is evaporated under vacuum and the residue is treated with ¹ H ₂ O (20 ml). The aqueous solution is extracted with CH ₂ Cl ₂ (3 x 20 mL) and dried over Na ₂ SO ₄ . The organic phase is evaporated under vacuum and purified by chromatography on silica with hexane / ethyl acetate (95/5) eluent to give a white solid. (160 mg, 80%). ¹ H NMR (CDCl ₃ ): δ = 1.27 ppm (s, 18H, t-Bu), 3.16 (t, J = 4.9 Hz, 4H, CH ₂ ), 3.71 (t, J = 4.9 Hz, 4H). , CH ₂ ), 6.98 (m, 8H), 7.43 (m, 10H), 8.12 (d, J = 2.4 Hz, 2H ₁ ), 9.86 (s, 2H), 11.15 (s, 2H). . ¹³ C NMR (63 MHz, CDCl ₃ ): δ = 31.21, 34.31, 63.21, 70.82, 84.52, 114.23, 114.57, 120.83, 129.19, 130.47, 130.60, 131.22, 133.08, 137.17, 156.74, 159.93, 163.88, 196.22. C ₅₂ H ₅₀ O ₇ F ₄ (863): hold. (+ 0.7 CH ₂ Cl ₂ ). C 68.62, H 5.62; found C 68.77, H 5.41. MS (DCI / NH ₃ ) m / z = 880 [M + NH ₄ ⁺ ].

Complex Mn '"- Salen 32:

Complex 32 is obtained as complex 18 from (82 mg, 0.10 mmol) in 40 mL of EtOH, (1S, 2S) - (+) - 1,2-diaminocyclohexane (11.8 mg,

0.10 mmol) and Mn (OAc) ₂ -4H ₂ O (25.6 mg, 0.10 mmol). Yield: 85 mg, 83% dark brown microcrystalline solid. C ₅₈ H ₅₈ N ₂ O ₅ F ₄ CIMn (1029.5): hold. (+ 0.2 CH ₂ CI ₂ )

C 66.8, H 5.63, N 2.68, Mn 5.26, Cl 3.40; found C 66.55, H 5.86, N 2.42, Mn 5.18,

Cl 3.84. MS (ES): m / z = 993.75 [M - Cl ^{"] +} IR (KBr, ^{cm." 1):} 1615 (C = N). UV / Vis (CH ₃ OH): λ (ε) = 276 nm (19463 MorW), 330 (9743), 420 (4417). [α] _D ²⁰ = 71.5 deg cm ² g ^'1 (c = 0.056 x ^{10 -3} g / ml, CH ₃ OH).

Example L: Preparation of Complex 33:

Schiff Base 34:

To 510 mg (0.94 mmol) of compound 17, dissolved in 50 ml of absolute EtOH, 110 mg of (1S, 2S) - (+) - 1,2-diaminocyclohexane (0.94 mmol) are added. The reaction medium is refluxed under nitrogen for 2 hours. After cooling, 50 ml of H ₂ O are added and the Schiff base precipitates. It is filtered, taken up in CH ₂ Cl ₂ (150 ml), washed with ¹ H ₂ O (150 ml) and dried over Na ₂ SO ₄ . The solvent was evaporated and the reaction crude was purified by chromatography column using hexane / ethyl acetate / triethylamine eluent (250 mL / 100 mL / 1 mL). Yield: 386 mg, 80% as a yellow solid. ¹ H NMR (CDCl ₃ ): δ = 1.22 ppm (s, 18H, t-Bu), 1.53 (s, 6H, CH ₃ ), 1.65 (s, 6H, CH ₃ ), 1.26-1.46 (m. , 4H), 1.60-1.88 (m, 4H), 3.29-3.33 (m, 2H), 3.50-3.66 (m, 4H, CH ₂ ), 3.73-3.89 (m, 4H, CH ₂ ) , 7.02 (d, J = 2.3 Hz, 2H), 7.62 (d, J = 2.3Hz, 2H), 8.31 (s, 2H, CH = N), 13.64 (s, 2H, OH). ¹³ C NMR (63 MHz, CDCl ₃ ) M = 24.38, 25.30, 27.81, 31.40, 33.34, 34.03, 62.05, 71.28, 72.53, 118.15, 126.66, 127.56, 132.45, 140.34, 156.43, 165.54. C ₃₈ H ₅₆ N ₂ O ₅ (620.9): hold. (+1 hexane 1 ethyl acetate) C 72.46, H 9.81, N 3.52; found C 72.25, H 9.54, N 3.76. MS (ES): m / z = 621.9 [M + H ⁺ f, 515.8 [M - (C ₄ H ₁₀ O ₃ ) + H ⁺ ] ⁺ . IR (KBr, cp ¹ ): 1628 (C = N). Complex Co '"- Salen 33: (ref .: used for the preparation of the complex

33: M. Tokunaga, J. F. Larrow, F. Kakiuchi, E. N. Jacobsen, Science,

1997, 277, 936-938).

The ligand 34 (93 mg, 1.50 mmol) dissolved in toluene (8 mL) was added cobalt (II) acetate tetrahydrate (37.3 mg, 1.5 mmol) dissolved in ¹ I absolute EtOH (8 mL). The reaction mixture is heated for 4 hours under reflux. After cooling, 2 equivalents of acetic acid (11 .mu.l dissolved in 1 ml of EtOH) are added and the resulting solution is stirred for 15 hours in air. After evaporation of the solvents, the crude is dissolved in CH ₂ Cl ₂ (15 mL) and precipitated with hexane (50 mL). Yield: 94 mg, 80% as a brown solid. C ₄₂ H ₈ N ₂ O _{6 S} Co (782.9): calc. (+2H ₂ O) C 61.60, H 8.23, N 3.42; found C 61.89, H 7.95, N 3.65. MS (ES): m / z = 723.9 [Co ^π Salen (EtOH)] ⁺ , 783.9 [Co ^and Salen (OAc) (EtOH) + H ⁺ ] ⁺ . IR (KBr, error ¹ ): 1627 (C = N). UV / Vis (CH ₃ OH): λ (ε) = 228 nm (20190 L mol ^-1 cm ^-1 ), 262 (22760), 402 (3050). [α] _D ²⁰ = + 117 deg cm ² g ^-1 (c = 0.077 x 10 ^-3 g / mL, CH ₃ OH).

Example K: Preparation of Complex 35:

Compound 36:

To a solution of 13 (32.51 g, 93.4 mmol) in anhydrous diethyl ether (82 ml), under an inert atmosphere, a solution of n-Buϋ in hexane (1.6 is added dropwise and at -78 ^° C. M, 72 mL, 112.1 mmol). After stirring for 1 hour at this temperature, a yellow solution is obtained to which is added dropwise and at -78 ⁰ C a solution of 3-pentanone previously dried over molecular sieve 4 A (12.83 mL, 121.4 mmol) in anhydrous ether (10 mL) (still under an inert atmosphere). Stir 1 hour at -78 ⁰ C and then allow the mixture to return to room temperature. Water is then added at 50 ^° C. The mixture is extracted with ether (3 × 300 mL). The organic phases are combined, washed with water (2 × 300 mL) and dried over Na ₂ SO ₄ . The solvent is evaporated and the crude reaction product is purified by chromatography column using hexane / ethyl acetate (98/2) as eluent, a colorless oil (15.17 g, 45%) is then obtained. ¹ H NMR (CDCl ₃ ): δ = 0.79 ppm (t, 6H ₁ CH ₃ ), 1.27 (s, 9H, t-Bu), 1.73-1.97 (m, 4H, CH ₂ ), 4.22 (s, 1 H, OH), 4.57 (d, J = 5.5 Hz, 2H), 5.44 (dd, ³ J = 17 Hz, ⁴ J = 1.6 Hz 2 H), 5.51 (d, ³ J = 17 Hz, ⁴ J = 1.6 Hz, 2H), 6.12 (m, 1H), 7.16 (d, J = 2.0 Hz, 1H), 7.43 (d, J = 2.0 Hz ₁ 1 H). ¹³ C NMR (63 MHz, CDCl ₃ ) δ = 8.24, 31.23, 34.40, 34.85, 74.71, 79.26, 117.52, 118.26, 124.98, 129.24, 132.90, 138.46, 147.94, 151.26. C ₁₈ H ₂₇ O ₂ Br ₁ (354): hold. C 60.85, H 7.66; found C 60.86, H 7.60. MS (EI): m / z (%) = 354 [M].

Compound 37:

The NaH (6.37 g of a 60% suspension in oil, 159.3 mmol) is washed with pentane (2 × 20 mL) and then suspended in THF (50 mL), then, under nitrogen, is added dropwise a solution of 36 (12.85 g, 36.2 mmol) in THF (50 mL). The mixture is stirred for 1 h at room temperature. Then, a solution of diethylene glycol ditosylate (7.50 g, 18.1 mmol) in anhydrous DMF (26 mL) is added all at once. The reaction is monitored by TLC (hexane / ethyl acetate: 9/1) and ¹ H NMR (CDCl ₃ ) to determine the amount of remaining compound 36 and the consumption of triethylene glycol ditosylate. After 15 h, 2.70 g of diethylene glycol ditosylate (6.51 mmol) dissolved in DMF (5 mL) are added and the reaction medium is stirred for 24 h. Saturated NaCl solution (100 mL) is added and then extracted with CH ₂ Cl ₂ (3 x 100 mL). The organic phases are combined, washed with water (2 × 100 mL), dried over Na ₂ SO ₄ , filtered and concentrated. The reaction crude is dissolved in MeOH (250 mL) and the resulting solution placed at -20 ^° C. for the night. The white precipitate thus obtained is filtered and dried under vacuum (4.47 g, 32%). ¹ H NMR (CDCl ₃ ): δ = 0.64 ppm (t, 12H, CH ₃ ), 1.27 (s, 18H, f-Bu), 2.00 (q, J = 7.3 Hz, 8H, CH ₂ ), 3.44 (t, J = 5.2 Hz, 4H, CH ₂ ), 3.83 (t, J = 5.2 Hz, 4H, CH ₂ ), 4.50 (d, J = 5.3 Hz, 4H), 5.28 (dd, ³ J = 10 Hz, ⁴ J = LO Hz, 2H), 5.44 (dd, ³ J = U Hz, ⁴ J = 1.5 Hz, 2H), 6.05-6.21 (m, 2H), 7.43 (d, J) = 2.4 Hz, 2H, ArH), 7.66 (d, J = 2.4 Hz, 2H, ArH). ¹³ C NMR (6 3 MHz, CDCl _3.): Δ = 7.97, 27.52, 31.29, 34.47, 60.40, 71.30, 73.40, 81.93, 117.26, 117.37, 126.74, 129.74, 133.63, 137.56, 147.15, 150.56. C ₄₀ H ₆₀ O ₅ Br ₂ (778.3): hold. C 61.54, H 7.75; found C 61.80, H 7.79. MS (FAB, MNBA): m / z (%) = 803 [M + Na ⁺ ] ⁺ .

Compound 38:

To a solution of 37 (1.0 g, 1.28 mmol) in anhydrous ether (3 mL) at -90 ^° C., a mixture of n-BuLi (1.6 M, 3.2 mL, 5.12 mmol) is added dropwise under an inert atmosphere. ) and TMEDA (0.88 mL, 5.79 mmol) in anhydrous ether (3 mL). The yellow solution obtained is stirred at -90 ^° C. for 30 min. Then, a solution of anhydrous DMF ((0.99 mL, 12.8 mmol) in ether (3 mL) is added at -90 ° C., still under an inert atmosphere, then the mixture is allowed to warm to -40 ° C. and then Remove the bath and stir for a further 10 minutes Water is added at -10 ° C. The mixture is extracted with ether (3 × 50 ml), the organic phases are combined and washed with water. water (2 x 50 mL) and dried over Na ₂ SO _4. After evaporation of the solvent, the crude reaction product is dissolved in a mixture of ethyl / hexane (30 mL / 30 mL) and placed at -20 ^° C. for the night. After filtration and drying, the white solid is directly used for the next step: ¹ H NMR (CDCl ₃ ): δ = 0.62 ppm (t, 12H, CH ₃ ), 1.30 (s, 18H, t-Bu) ), 1.90-2.10 (m, 8H, CH ₂ ), 3.45 (t, J = 5.5 Hz, 4H, CH ₂ ), 3.74 (t, J = 5.5 Hz, 4H, CH ₂ ), 3.76 (s, , 4H, CH ₂ ), 4.41 (dd, ³ J = 3.7 Hz, ⁴ J = 1.5 Hz, 4H), 5.29 (dd, ³ J = 9.1 Hz, ⁴ J = 1.2 Hz, 2H), 5.49 (dd, ³ J = 9.1 Hz, ³ J = L 2 Hz, 2H), 5.99-6.12 (m, 2H), 7.73 (d, J = 2.9 Hz ₁ 2 H) 7.96 (d, J = 2.9 Hz, 2H) 10.26 (s, 2H).

Compound 39: To a solution of 38 (530 mg 0.781 mmol) in MeOH (15 mL) was added, under an inert atmosphere, catalytic amounts of Pd (PPh ₃ ) ₄ (45.0 mg, 0.391 mmol). Then stirred 5 min. and K ₂ CO ₃ (647.37 mg, 4.684 mmol) is added. The reaction is followed by TLC. After stirring for 1 hour, it is finished. The crude reaction is concentrated; a solution of 1N HCl is then added to adjust the pH to 6-7. The aqueous phase is extracted with CH ₂ Cb (3 x 50 mL), washed with I ¹ H ₂ O (2 x 50 mL) and dried over Na ₂ SO ₄ . After evaporation of the solvent, the crude reaction product is concentrated and purified by chromatography using the pentane / ethyl acetate system (96/4). A white solid (707 mg, 80%) is obtained. ¹ H NMR (CDCl ₃ ): δ = 0.68 ppm (t, 12H, CH ₃ ), 1.29 ppm (s, 18H, f-Bu), 1.88-2.15 (m, 8H, CH ₂ ), 3.54 ( t, J = 5.1 Hz, 4H, CH ₂ ), 3.84 (t, J = 4.7 Hz, 4H, CH ₂ ), 7.50 (d, J = 2.5Hz), 2H), 7.67 (d, J = 2.5 Hz, 2H), 10.11 (s, 2H), 10.81 (s, 2H). ¹³ C NMR (63 MHz, CDCl ₃ ): δ = 7.71, 26.96, 31.23, 34.13, 60.34, 70.90, 83.52, 121.33, 126.40, 129.44, 133.71, 141.44, 157.53, 194.70. C ₃₆ H ₅₄ O ₇ (598.8): hold. C 72.22, H 9.09; found C 71.93, H 9.37. MS (ES) m / z (%) = 621.8 [M + Na ⁺ ] ⁺ , 637.8 [M + K ⁺ ] ⁺ .

Mn "- salen complex 35:

The complex is synthesized according to the procedure described above for complex 18, from a solution of 39 (80 mg, 0.0134 mmol) in 80 mL of EtOH, (1S, 2S) - (+) - 1 2-diaminocyclohexane (15.3 mg,

0.0134 mmol) and Mn (OAc) ₂ -4H ₂ O (32.8 mg, 0.0134 mmol). Yield: 87 mg, 85% as a microcrystalline solid. C ₄₂ H ₆₂ N ₂ O ₅ CIMn (765.4): hold. (+1

EtOH +1 H ₂ O) C 63.72, H 8.51, N 3.38, Mn 6.62, Cl 4.27; found C 63.69, H 8.59,

N 3.44, Mn 6.80, Cl 4.39. MS (ES): m / z = 730.4 [M-CP] ⁺ , 788.4 [M + Na ⁺ J ⁺ . IR

(KBr, errf ¹ ): 1613 (C = N). UV / Vis (CH ₃ OH): λ (ε) = 220 nm (40370 L mol ^-1 cm ^-1 ), 244

(37400), 293 (14650), 327 (9500), 357 (6440), 409 (4010). [α] _D ²⁰ = + 250 deg cm ² g ^-1 (c = 0.044 x 10 ^-3 g / ml, CH ₃ OH). Example L: Preparation of the complex 40

Compound 41:

The NaH (4.23 g of a 60% oil suspension, 105.6 mmol) is washed with pentane (2 x 25 ml) and then, under nitrogen, a solution of 36 (8.53 g, 24.0 mmol) in THF (35 ml). The mixture is stirred for 1 h at room temperature. Then, a solution of triethylene glycol ditosylate (5.5 g, 12 mmol) in anhydrous DMF (20 mL) is added all at once. The reaction is monitored by TLC (hexane / ethyl acetate: 9/1) and ¹ H NMR (25OMHz-CDCl ₃ ) to determine the amount of remaining compound 36 and the consumption of triethylene glycol ditosylate. After 24 hours, 4.40 g of triethylene glycol ditosylate (9.60 mmol) dissolved in DMF (15 mL) are added and the reaction medium is stirred for 24 h. Saturated NaCl solution (100 mL) is added and then extracted with CH ₂ Cl ₂ (3 x 100 mL). The organic phases are combined, washed with water (2 × 100 mL), dried over Na ₂ SO ₄ , filtered and concentrated. The crude reaction product is purified by chromatography using hexane / ethyl acetate (9/1) as eluent. A colorless oil (4.86 g, 49%) is obtained. ¹ H NMR (CDCl ₃ ): δ = 0.61 ppm (t, 12H, CH ₃ ), 1.26 (s, 18H, t-Bu), 1.88-2.07 (m, 8H, CH ₂ ), 3.42 (t , J = 5.4 Hz, 4H, CH ₂ ), 3.71 (t, J = 5.4 Hz, 4H, CH ₂ ), 3.73 (s, 4H, CH ₂ ), 4.49 (d, J = 5.3 Hz, 4). H), 5.27 (dd, ³ J = 16 Hz, ⁴ J = IA Hz, 2 H), 5.43 (dd, ³ J = 16 Hz, ⁴ J = IA Hz, 2H), 6.04-6.19 (m, 2H), 7.41 (d, J = 2.5Hz, 2H, ArH), 7.59 (d, J = 2.5Hz, 2H, ArH). ¹³ C NMR (63 MHz, CDCl ₃ ): δ = 7.96, 27.49, 31.29, 34.47, 60.26, 70.95, 71.14, 73.40, 81.98, 117.26, 117.37, 126.69, 129.31, 133.64, 137.55, 147.15, 150.56. C ₄₂ H ₆₄ O ₆ Br ₂ (824.8): hold. C 61.16, H 7.81; found C 61.26, H 7.46. MS (IE): m / z (%) = 824 [M]. Compound 42:

To a solution of 41 (2.25 g, 2.73 mmol) in anhydrous ether (155 ml) at -90 ^° C., a mixture of π-BuLi (1.6 M, 6.9 ml, 11 ml) is added dropwise under an inert atmosphere. mmol) and TMEDA (1.9 mL, 12.5 mmol) in anhydrous ether (6.5 mL). The yellow solution obtained is stirred at -90 ^° C. for 30 min. Then, a solution of anhydrous DMF (2.12 mL, 27.3 mmol) in ether (6.5 mL) is added at -90 ^° C., still under an inert atmosphere. Then the mixture is allowed to return to -40 ^° C., then the bath is removed and the mixture is stirred for a further 10 minutes. Water is added at -10 ^° C. The mixture is extracted with ether (3 × 100 ml), the organic phases are combined and washed with water (2 × 100 ml) and dried over water. Na ₂ SO 4 After evaporation of the solvent, a colorless oil (1.98 g) is obtained. The reaction crude is directly used for the next step. ¹ H NMR (CDCl ₃ ): δ = 0.62 ppm (t, 12H, CH ₃ ), 1.30 (s, 18H, t-Bu), 1.90-2.10 (m, 8H, CH ₂ ), 3.45 (t , J = 5.5 Hz, 4H, CH ₂ ), 3.74 (t, J = 5.5 Hz, 4H, CH ₂ ), 3.76 (s, 4H, CH ₂ ), 4.41 (dd, ³ J = 3.7 Hz, ⁴ J = I.5 Hz, 4H), 5.29 (dd, ³ J = 9.1 Hz, ⁴ J = 1.2 Hz, 2H), 5.49 (dd, ³ J = 9.1 Hz, ³ J = 1.2 Hz, 2H), 5.99 -6.12 (m, 2H), 7.73 (d, J = 2.9 Hz, 2H) 7.96 (d, J = 2.9 Hz, 2H) 10.26 (s, 2H).

Compound 43: To a solution of 42 (1.98 g, 2.74 mmol) in MeOH (56 mL) was added, under an inert atmosphere, catalytic amounts of Pd (PPh ₃ ) ₄ (158.2 mg, 0.137 mmol). Then stirred 5 min. and K ₂ CO ₃ (2.27 g, 16.44 mmol) is added. The reaction is monitored by TLC. After stirring for 1 hour, it is finished. The crude reaction is concentrated; a solution of 1N HCl is then added to adjust the pH to 6-7. The aqueous phase is extracted with CH ₂ Cl ₂ (3 x 100 mL), washed with I ¹ H ₂ O (2 x 100 mL) and dried over Na ₂ SO ₄ . After evaporation of the solvent, the crude reaction product is concentrated and purified by chromatography using the pentane / ethyl acetate system (9/1). A colorless oil (1.43 g, 81%) is obtained. ¹ H NMR (CDCl ₃ ): δ = 0.64 ppm (t, 12H, CH ₃ ), 1.28 ppm (s, 18H, t-Bu), 1.88-2.12 (m, 8H, CH ₂ ), 3.50 ( t, J = 4.9 Hz, 4H, CH ₂ ), 3.75 (t, J = 4.9 Hz, 4H, CH ₂ ), 3.75 (s, 4H, CH ₂ ), 7.49 (d, J = 2.4 Hz, 2H), 7.66 (d, J = 2.4 Hz, 2H), 10.10 (s, 2H), 10.80 (s, 2H). ¹³ C NMR (63 MHz, CDCl ₃ ): δ = 7.67, 26.86, 31.22, 34.09, 60.20, 70.63, 71.03, 83.40, 121.28, 126.4, 129.51, 133.72, 141.46, 157.46, 194.72. C ₃₈ H ₅₈ O ₈ (642.9): hold. C 71.00, H 9.09; found C 70.79, H 9.28. MS (ES) m / z (%) = 665.85 [M + Na ⁺ ], 681.65 [M + K ⁺ ] -

Schiff Base 44:

To 200 mg (0.311 mmol) of compound, dissolved in 50 ml of absolute EtOH, 88.5 mg of (S) - (-) - 1, 1'-binaphthyl-2,2'-diamine (0.311 mmol) are added. Na 2 SO ₄ are added in excess. The reaction medium is refluxed under nitrogen for 27 h and then concentrated to 10 mL. The Schiff base precipitates. It is filtered hot, washed with I ¹ EtOH (20 mL) then extracted with CH ₂ Cl ₂ (50 mL), and dried. Yield: 140 mg, 51% as an orange solid. ¹ H NMR (CDCl ₃ ): δ = 0.35 ppm (t, J = 7.3 Hz, 6H, CH ₃ ), 0.37 (t, J = 7.3 Hz, 6H, CH ₃ ), 1.18

(s, 18H, t-Bu), 1.58-1.75 (m, 4H, CH ₂ ), 1.81-1.99 (m, 4H, CH ₂ ), 3.41 (t, J = 5.3

Hz, 4H, CH ₂ ), 3.68 (m, J = 5.3 Hz, 4H, CH ₂ ), 3.74 (s, 4H, CH ₂ ), 7.00 (d, J = 2.3

Hz, 2H), 7.28-7.33 (m, 4H), 7.40 (t, J = 7.4 Hz, 2H), 7.54 (d, J = 8.8 Hz, 2).

H), 7.59 (d, J = 2.8 Hz, 2H), 7.92 (d, J = 8.8 Hz, 2H), 8.01 (d, J = 8.8 Hz, 2H), 8.57 (s, 2H, CH); = N), 12.61 (s, 2H, OH). ¹³ C NMR (63 MHz, CDCl ₃ ): δ = 7.80,

26.06, 31.30, 33.87, 59.92, 71.07, 71.19, 81.48, 116.98, 117.80, 125.44, 126.54,

126.73, 128.06, 129.17, 129.61, 129.98, 130.91, 132.48, 133.33, 133.83, 139.62,

143.95, 155.93, 162.41. C ₅₈ H ₇₀ N ₂ O ₆ (891.2): hold. (+ 1H ₂ O) C 76.62, H, 7.98, N 3.08; found C 76.32, H 7.73, N 3.06. MS (ES): m / z = 891.85 [M + H ⁺ ] ⁺ , 914.05 [M + Na ⁺ ] ⁺ . IR (KBr ₁ cp ¹ ): 1611 (C = N).

Mn "- Salen 40 complex: Compound 43 (200 mg, 0.311 mmol) is dissolved under an inert atmosphere in 15 ml of EtOH, and then (S) - (-) - 1, 1 'is added successively. -benzaphthyl-2,2'-diamine (88.5 mg, 0.311 mmol) and manganese (II) diacetate tetrahydrate (114.5 mg, 0.467 mmol) After stirring under reflux for one night under an inert atmosphere, the mixture is bubbled through. air in the solution for 2 h The mixture is concentrated to 20 ml, then 30 ml of saturated NaCl solution are added and the mixture is extracted with 2x50 ml of CH ₂ Cl _2, the organic phase is then washed with 2 × 50 ml of H ₂ O and dried over Na ₂ SO _4. After evaporation of the solvent, the product is redissolved in CH ₂ Cl ₂ (10 mL) and precipitated with pentane (100 mL). After filtration and drying under vacuum, the complex 40 (120 mg, 40%) is obtained as a microcrystalline brown solid C ₅₈ H ₆₈ N ₂ O ₆ CIMn (979.6): Cale 71.12, H 7.00, N 2.86, found C 71.13, H 7.01, N 3.11 . MS (ES): m / z = 975.85 [Mn SalenCI ^m + H ⁺ ] ⁺ , 989.85 [Mn ⁺ 'Salen (EtOH) - CP] ⁺ . IR (KBr, cm- ¹ ): 1610 (C = N), UV / Vis (CH ₂ Cl ₂ ): λ (ε) = 233 nm (89,400 L morW ¹ ), 282 (49,300), 327 (24400), 388 (15400). [Α] _D ²⁰ = + 588 deg cm ² g ^-1 (c = 0.08 x 10 ^-3 g / ml, CH ₂ Cl ₂ ).

Example M: Preparation of complex 45: (ref: used for the preparation of complex 45: T. Uchida, T. Katsuki, Helvetica Chimica Acta, 2002, 85, 3078-3089).

Complex Co '"- Salen 45:

The cobalt diacetate tetrahydrate (77.5 mg, 0.311 mmol) is dissolved, under an inert atmosphere, in 4 ml of anhydrous DMF and then heated under vacuum at 80 ^° C. until a purple color is obtained. Subsequently, compound 43 (200 mg, 0.311 mmol) dissolved in 1 mL of anhydrous DMF and (S) - (-) - 1, 1'-binaphthyl-2,2'-diamine (88.52 mg, 0.311) are added successively. mmol) dissolved in 1 mL of anhydrous DMF under an inert atmosphere. The reaction mixture is heated at 80 ° C for 24 hours. After evaporation of the solvent, the crude is dissolved in CH ₂ Cl ₂ (5 mL) and precipitated with hexane (200 mL). After filtration, the product is dried under vacuum and 230 mg (78%) of cobalt (II) complex is obtained in the form of a microcrystalline brown solid. To the complex of cobalt (II) (230 mg, 0.243 mmol) dissolved in CH ₂ Cl ₂ (7 mL) are added 30.83 mg of I ₂ (0.1214 mmol). After stirring for 1 hour, 343.61 mg of AgSbF ₆ (0.243 mmol) are added and the reaction medium is stirred for 6 h and then filtered through Celite. After evaporation of the solvent, the complex 45 is dried under vacuum. A brown powder (190 mg, 52%) is obtained. C ₅₈ H ₆₈ N ₂ O ₆ CoSbF ₆ (1183.8): hold. (+1 CH ₂ Cl ₂ ) 55.85, H 5.56, N 2.21; found C 56.03, H 5.78, N 2.26. MS (ES): m / z = 970.85 [Co "(Salen) + Na ⁺ J ⁺ , 978.75 [Co '" (Salen) + MeOH)] ⁴ . IR (KBr, cm- ¹ ): 1635 (C = N), UVΛ / is (CH ₂ Cl ₂ ): λ (ε) = 229 nm (78800 L morW ¹ ), 281 (29500), 347 (23700), 427 (12800). [Α] _D ²⁰ = -2025 deg cm ² g ^-1 (c = 0.08 x lu ^-3 g / ml, CH ₃ OH).

II - Procedures for catalytic epoxidation. With sodium hypochlorite as oxidant:

A typical reaction medium contains the substrate (14 μl for 1,2-dihydronaphthalene, 16 μl for 2,2'-dimethylchromene and 13 μl for cis-β-methylstyrene, 0.1 mmol) and an internal standard (23.6 mg of 1, 4-dibromobenzene with 1,2-dihydronaphthalene or 2,2'-dimethylchromene as substrate and 19.5 μl of 7-decane with c / s-β-methylstyrene as substrate, 0.1 mmol) in 0.5 ml of CH ₂ Cl ₂ , 5 μmol of the appropriate catalyst (0.5 ml of a 10 mM stock solution in CH ₂ Cl ₂ , catalyst / substrate ratio = 5%) and 4-phenylpyridine N-oxide (4.3 mg, 25 μmol) when specified . After stirring at ambient temperature or at 0 ^° C. for 10 min, 0.2 mmol of NaOCI (0.4 ml of a 0.5M aqueous solution of NaOCI plus 0.16 ml of a 0.05 M aqueous solution of Na ₂ HPO ₄ , 2 eq of oxidizing with respect to the ^'substrate) was added. After vigorous stirring for 2 h, the reaction medium is diluted with water (2 mL) and CH ₂ Cl ₂ (2 mL). The phases are separated, the organic phase dried over Na ₂ SO ₄ , concentrated to ≈ 1 mL and analyzed by gas chromatography with a Supelco cyclodextrin-β capillary column (betadex 120, 30m × 0.25 mm, 0.25 μm film). Absolute configurations are assigned by comparison with the values of αp data in the literature.

With iodosylbenzene as oxidant (ref for the preparation of iodosylbenzene: Saltzman, H. et al., Organic Syntheses, 1973, 5, 658):

The reaction medium is prepared according to the protocol described above. After stirring at room temperature or at 0 ^° C. for 10 min, PhIO (44 mg, 0.2 mmol, 2 eq of oxidant relative to the substrate), MeOH (225 μL) and water (25 μL) are added. After stirring for 2 h, the reaction medium is diluted with CH ₂ Cl ₂ (2 mL) and filtered through Celite. The filtrate is treated as before and analyzed in chiral GC.

With 7-tetrabutylammonium hydrogen sulfate as an oxidizer (ref for the preparation of n-tetrabutylammonium hydrogen sulfate: P.Hoffman et al., Bull Soc ChIm, Fr., 1992, 129, 85): The reaction medium is prepared according to the protocol described above but the substrate and the catalyst are dissolved in CH ₃ CN (total volume 1 ml) in place of CH ₂ Cl ₂ . After stirring at 0 ^° C. for 10 min, H-Bu ₄ NHSO ₅ (71 mg, 0.2 mmol, 2 eq of oxidant relative to the substrate) is added. After stirring for 30 minutes, the reaction medium is trapped with sodium dithionite, diluted with CH ₃ CN (2 ml) and filtered through Celite. The filtrate is treated as before and analyzed in chiral GC.

With hydrogen peroxide as oxidant: The reaction medium is prepared according to the protocol described above. After stirring at 0 ^° C. for 10 min, 35% aqueous H ₂ O ₂ (16 μl, 0.3 mmol, 3 eq of oxidant relative to the substrate) is added in four portions over 40 min. After stirring for 2 h, the reaction medium is diluted with I ¹ H ₂ O (2 mL) and CH ₂ Cl ₂ (2 mL). The filtrate is treated as before and analyzed in chiral GC.

With m-chloroperbenzoic acid:

The reaction medium is prepared according to the protocol described above. After stirring at -78 ° C for 10 min, m-CPBA (17.3 mg, 0.2 mmol, 2 eq of oxidant relative to the substrate) is added. After stirring for 2 h at -78 ° C., the reaction medium is diluted with FH ₂ O (2 mL) and CH ₂ Cl ₂ (2 mL). The filtrate is treated as before and analyzed in chiral GC.

EXAMPLES 1-9: Asymmetric epoxidation of 1,2-dihydronaphthalene with first-generation catalysts 3-6, 8 and 11 and sodium hypochlorite.

catalyst (5 mol%) oxidizing (2 eq)

Table I

The reactions are carried out with the substrate (0.1 mmol), the catalyst (5 μmol) and the oxidant (0.2 mmol) at room temperature, unless mentioned. ^has epoxide yield (yield of naphthalene). ^b Epoxy selectivity. ^c Enantiomeric excesses (= ee) are determined by chiral GC; the configurations of the epoxides are 1S.2R for catalysts 3, 5, 8 and 11 and 1f, 2S for catalysts 4 and 6. ^d The reactions are carried out at 0 ^° C. in the presence of 5 eq. of 4-PPNO relative to the catalyst.

The best results are obtained for the catalyst 8.

EXAMPLES 10-17: Asymmetric epoxidation of c / s-disubstituted olefins with catalyst 8 and various oxygen atom donors.

Table II

The reactions are carried out with the substrate (0.1 mmol), the catalyst (5 μmol) and the oxidant (0.2 mmol) at 0 ^° C. in the presence of 5 eq. of 4-PPNO relative to the catalyst, unless mentioned. ^has epoxide yield (yield of naphthalene). ^b Selectivity of the desired epoxide. ° ee are determined by chiral CG; the configurations of the epoxides are 3S, 4R for dimethylchromene and

1R, 2S for 1,2-dihydronaphthalene. The reactions are carried out at room temperature. ^e 1% catalyst.

The best results are obtained with the catalyst system 8 / PhlO / 4-

PPNO / 0 ° C for the epoxidation of 2,2'-dimethylchromene.

EXAMPLES 18-29: Asymmetric epoxidation of c / s-disubstituted olefins with the second generation catalyst 18 and various oxygen atom donors.

Board

The reactions are carried out with the substrate (0.1 mmol), the catalyst (5 μmol) and the oxidant (0.2 mmol) at 0 ^° C. in the presence of 5 eq. of 4-PPNO relative to the catalyst, unless mentioned. ^has epoxide yield (yield of naphthalene or trans - $ - methylstyrene oxide). ^b Selectivity of the desired epoxide. ° ee are determined by chiral CG; the epoxide configurations are 3R, 4R for 2,2'-dimethylchromene and 1R, 2S for 1,2-dihydronaphthalene and c / s-β-methylstyrene. ^d The reactions are carried out at room temperature. ^s 1% catalyst / oxidant 0.3 mmol (3 eq. relative to the substrate). ^s The reaction is performed at -80 ° C for 30 min.

EXAMPLES 30-32: Effect of the axial ligand on the asymmetric epoxidation of 2,2'-dimethylchromene with the catalyst 18

Table IV

The reactions are carried out with 2,2'-dimethylchromene (0.1 mmol), the catalyst (5 μmol) and NaOCI as oxidant (0.2 mmol) at 0 ^° C. in the presence of 5 eq. of axial ligand with respect to the catalyst. ^a Epoxy yield. ^b ee are determined by chiral CG; the configuration of the epoxide is not determined for 2,2'-dimethylchromene.

4-PPNO is retained as the best axial ligand.

EXAMPLES 33-41: Catalyst Recycling 18.

Table V

The reactions are carried out with the substrate (0.1 mmol), the catalyst

(5 μmol) and NaOCI as oxidant (0.2 mmol) at 0 ^° C. in the presence of 5 eq. of 4 PPNO with respect to the catalseur. ^has epoxide yield (yield of naphthalene). ^b Selectivity of the desired epoxide. ^c ee are determined by chiral GC; the configurations of the epoxides are 3R, 4R for 2,2'-dimethylchromene and 1R, 2S for 1,2-dihydronaphthalene.

Catalyst 18 (5 mol%) can be recycled three times without significant loss of activity and enantioselectivity.

The reaction is carried out with the substrate (0.1 mmol), the catalyst (1 μmol) and NaOCI as oxidant (0.2 mmol) at room temperature in the presence of 5 eq. of 4-PPNO relative to the catalyst. ^has epoxide yield (yield of naphthalene). ^b Selectivity of the epoxide. ^c ee are determined by chiral GC; the configuration of the epoxide is 1R, 2S for 1, 2-dihydronaphthalene.

Catalyst 18 (1 mol%) can be recycled twice without loss of activity; the number of catalytic cycles is 231.

EXAMPLE 42: Asymmetric epoxidation of 2,2'-dimethylchromene with a low catalyst load (18).

Table VI

The reaction is carried out with the substrate (0.1 mmol), the catalyst (0.05 μmol) and NaOCI as oxidant (0.2 mmol) at room temperature in the presence of 5 eq. of 4-PPNO relative to the catalyst. The ee ^was determined by chiral GC; the configuration of the epoxide is 3R, 4R for 2,2'-dimethylchromene.

Catalyst 18 can carry out 1040 catalytic cycles.

EXAMPLES 43-51: Effect of the groups of catalysts of m = 1 type in asymmetric epoxidation.

Table VII

The reactions are carried out with the substrate (0.1 mmol), the catalyst (5 μmol) and NaOCI as oxidant (0.2 mmol) at 0 ^° C. in the presence of 5 eq. of 4-PPNO relative to the catalyst. ⁸ epoxide yield (yield of trans-β-methylstyrene oxide). ^b Selectivity of the desired epoxide. ^c ee are determined by chiral GC; the configurations of the epoxides are 3R, 4R for 2,2'-dimethylchromene and 1f, 2S for c / s-β-methylstyrene.

Complex 18 is the best m = 1 type catalyst.

III - Procedure for the kinetic resolution of hydrolysis of a racemic epoxide (ref: used: J. F. Larrow, K. E. Hemberger, S. jasmine, H. Kabir, P. Morel, Tetrahedron Asymmetry, 2003, 14, 3589-3592).

The reaction medium contains styrene oxide (45.6 μL, 0.4 mmol), catalyst 33 (6.26 mg, 8 μmol), catalyst / substrate ratio = 2%) and I ¹ H ₂ O (5 μL, 0.28 mmol, 0.7 equivalent per relative to the substrate). After stirring for 44 h at room temperature, 1 mL of CH ₂ Cl ₂ and Na ₂ SO ₄ are added. After filtration, the organic phase is analyzed by gas chromatography with a Supelco cyclodextrin-β capillary column (betadex 120, 30m × 0.25 mm, 0.25 μm film) in the presence of 1, 2,4-trichlorobenzene as internal standard (30 μL, 0.24 μm). mmol). Absolute configurations are assigned by comparison with the values of αo given in the literature.

EXAMPLE 52

Table VIII

The reaction is carried out with the substrate (0.4 mmol), the catalyst (8 μmol) and I ¹ H ₂ O (0.28 mmol) at room temperature. ^a The enantiomeric excess (= ee) are determined by chiral GC; the majority configurations are S-epoxide and f-1, 2-diol.

Asymmetric epoxidation of c / s-disubstituted olefins with catalyst 35

EXAMPLES 53-55

Table IX

The reactions are carried out with the substrate (0.1 mmol), the catalyst (5 δmol) and NaOCI (0.2 mmol) at 0 ^° C. in the presence of 5 eq. of 4-PPNO relative to the catalyst. ^has epoxide yield (yield of naphthalene or trans-D-methylstyrene). ^b ee are determined by chiral CG.

The catalyst gives the best enantiomeric excesses.

Claims

1. Chiral compounds of formula (I):

(I)

- in which:

M represents a metal atom or a salt of this atom;

L represents a neutral or anionic ligand;

• A and A ', chiral, identical or different, independently represent a chain of type (-CR8 _a R9 _a -) a and (-CR8' _a 'R9' _a -) a 'respectively, where: is R8 _a and R9 _a and R8 ' _a > and R9' _a > are the same or different for each link (-CR8 _to R9 _a -) a and (-CR8 '_a' R9 ' _a ' -) a ', and independently represent an atom of hydrogen, aryl or heteroaryl, or is _R8 and R8 _'has, respectively R9 _is and R9 _has taken together with the carbon atoms to which they are attached a cycloalkyl group and R 9 _a and R 9' _{a ', R8} respectively R8V and represent a hydrogen atom, or either two of _R8 and / or R9 _is consecutive, respectively R8 _'has and / or R9' consecutive _has taken together with the carbon atoms to which they are attached form an optionally substituted aryl group, and wherein a and a ', which are identical or different, represent an integer chosen from 1 or 2;

R4, R4 ', R6, R6', which are identical or different, independently represent a hydrogen atom, a halogen atom or a -NO ₂ , -O-alkyl, -aryl or -alkyl group optionally substituted by one or more groups; chosen from halogen atoms and -OR, -CN, -NO ₂ , -NRR ', -COOR, perhaloalkyl, -aryl groups;

R5, R5 ', which may be identical or different, independently represent a halogen atom or a group -NO ₂ , -O-alkyl, -aryl, or -alkyl optionally substituted by one or more groups chosen from halogen atoms and the groups -OR, -CN, -NO ₂ , -NRR ', -COOR, perhaloalkyl, -aryl;

M, m 'represent O or 1;

R 10, R 11, R 10 ', R 11' - the same or different independently represent a hydrogen atom or a group selected from -alkyl, -aryl each optionally substituted by one or more halogen atoms;

- W and W, identical or different independently represent an oxygen atom or a group -NR-, -CRR'-, -SiRR'-;

X represents an alkyl chain, of 1 to 10 carbon atoms, preferably linear, optionally interrupted by one or more oxygen atoms or by one or more aryl groups, such as -alkyl-O-alkyl-, -alkyl- O-alkyl-O-alkyl-, etc., or -alkyl-aryl-alkyl-, -alkyl-aryl-alkyl-aryl-alkyl-, etc., where the alkyl chain is optionally perhalogenated, and wherein the aryl group is optionally substituted by one or more substituents, which may be identical or different, chosen from -OH, -O-alkyl, -COOR, -NRR ', -SO ₃ H, -S (O) pR, -NO ₂ , -CN;

- P = 0, 1 or 2;

R and R ', which may be identical or different, independently represent a hydrogen atom or an -alkyl group, optionally substituted with one or more substituents, which may be identical or different, chosen from -OR, -COOR, -NRR', -SO ₃ H, -S (O) pR, -NO ₂ , -CN; as well as the resulting mono-cationic complex, and optionally with its mono-anionic counterion.

2. Chiral compounds of formula (I):

(D in which:

M represents a metal atom or a salt of this atom;

"L represents a neutral or anionic ligand;

• A and A ', chiral, identical or different, independently represent a chain of the type (-CR8 _a R9 _a -) a and (-CR8' _a 'R9' _a -) a chiral respectively, where: either R8 _a and R9 _is and R8 _'a' and R9 _'a> are identical or different for each chain link (-CR8 R9 _{is a} -) a and (-CR8' _a 'R9' _a -) a ', and independently represent a hydrogen atom, hydrogen, aryl or heteroaryl, or is _R8 and R8 _'has, respectively R9 _is and R9 _has taken together with the carbon atoms to which they are attached a cycloalkyl group and R 9 _a and R 9' _a ', _R8 respectively and R8V represents a hydrogen atom, or and where a and a ', which are identical or different, represent an integer chosen from 1 or 2;

R4, R4 ', R6, R6', which may be identical or different, independently represent a hydrogen atom, a halogen atom or a group -NO2, -O-alkyl, -aryl, or

-alkyl optionally substituted by one or more groups selected from halogen atoms and -OR, -CN, -NO ₂ , -NRR ', -COOR, perhaloalkyl, -aryl; R5, R5 ', which may be identical or different, independently represent a halogen atom or a group -NO ₂ , -O-alkyl, -aryl, or -alkyl optionally substituted by one or more groups chosen from halogen atoms and the groups -OR, -CN, -NO ₂ , -NRR ', -COOR, perhaloalkyl, -aryl;

M, m 'represent O or 1;

• R10, R11, R10 ', R11' identical or different independently represent a hydrogen atom or a group selected from -alkyl, -aryl each optionally substituted by one or more halogen atoms;

- VV and W ₁ identical or different independently represent an oxygen atom or a group -NR-, -CRR'-, -SiRR'-;

X represents an alkyl chain, of 1 to 10 carbon atoms, preferably linear, optionally interrupted by one or more oxygen atoms or by one or more aryl groups, such as -alkyl-O-alkyl-, -alkyl- O-alkyl-O-alkyl-, etc., or -alkyl-aryl-alkyl-, -alkyl-aryl-alkyl-aryl-alkyl-, etc., where the alkyl chain is optionally perhalogenated, and wherein the aryl group is optionally substituted by one or more substituents, which may be identical or different, chosen from -OH, -O-alkyl, -COOR, -NRR ', -SO ₃ H, -S (O) pR, -NO ₂ , -CN;

- p = 0, 1 or 2;

- R and R ', which are identical or different, independently represent a hydrogen atom or an -alkyl group, optionally substituted by one or more substituents, which may be identical or different, chosen from -OR, -COOR, -NRR', -SO ₃ H, -S (O) pR, -NO ₂ , -CN; as well as the resulting mono-cationic complex, and optionally with its mono-anionic counterion.

3. A compound according to claim 1 or 2, such that M is an atom of Group IB, HB, IHB ₁ IVB, VB, VIB, VIIB, VIIIB or NIA.

4. A compound according to claim 1, 2 or 3 wherein M represents a group VIIB or VIIIB metal atom.

5. A compound according to claim 1, 2 or 3, such that (A) a and (A ') a' represent a link of type:

respectively, or their enantiomers.

or their enantiomers where

R8, R9 and R8 'and R9' are the same or different, and independently represent a hydrogen atom, an aryl or heteroaryl group, or R8 and R8 ', respectively R9 and R9' together with the carbon atoms to which they are attached a cycloalkyl group and R9 and R9 ', respectively R8 and R8' represent a hydrogen atom.

6. A compound according to any one of the preceding claims, such as R4 and R4 ', R5 and R5 \ R6 and R6', R7 and R7 \ R8 and R8 \ R9 and R9 ', R10 and R10 \ R11 and

R11 ', are equal to 2 to 2.

A compound according to any one of the preceding claims wherein L represents a halogen atom or a neutral ligand.

8. A compound according to any of the preceding claims wherein L is 4-phenylpyridine-Λ / -oxide.

9. Compound according to any one of the preceding claims, such that A and A ', which are identical, each represent a link of the type: respectively, or their enantiomers

or

R8 and R8 ', respectively R9 and R9', represent an aryl or heteroaryl group, or R8 and R8 ', respectively R9 and R9' together with the carbon atoms to which they are attached a cycloalkyl group and R9 and R9 ', respectively R8 and R8 'represent a hydrogen atom.

10. Compound according to any one of the preceding claims, wherein A and A ', which are identical, each represent a link of the type:

respectively, or their enantiomers where R8, R8 \ R9, R9 'are defined as above.

11. A compound according to any one of the preceding claims, such that R8 and R8 ', respectively R9 and R9', represent a phenyl group and

R9 and R9 ', respectively R8 and R8' represent a hydrogen atom, or, even more preferably, R8 and R8 ', respectively R9 and R9 together form a cycloalkyl and R9 and R9', respectively R8 and R8 'represent a hydrogen atom.

12. A compound according to any one of the preceding claims wherein R4, R4 ', R6, R6' represent a hydrogen atom.

13. A compound according to any one of the preceding claims, such that R5 and R5 ', which are identical, represent an alkyl group.

14. A compound according to any preceding claim such that m = m '= 1.

15. A compound according to any one of the preceding claims, such that R10, R11, R10 ', R11' are identical to a group selected from -alkyl, -aryl each optionally substituted with one or more halogen atoms.

16. A compound according to any preceding claim such that W and W, identical represent an oxygen atom.

17. A compound according to any one of the preceding claims wherein X represents a chain -alkyl-O-alkyl-, -alkyl-O-alkyl-O-alkyl-, etc. or -alkyl-aryl-alkyl-, -alkyl-aryl-alkyl-aryl-alkyl-, etc., where the aryl group is optionally substituted with -OH.

18. A compound according to any preceding claim as selected from

as well as the resulting mono-cationic complex, and optionally with its mono-anionic counterion.

19. A compound according to any preceding claim as selected from

^"As well as the mono-cationic resulting complex, and optionally with its monoanionic against ion.

Compound according to any one of the preceding claims as represented by the formula (I ¹ ):

or their enantiomers, wherein M, L, R8, R9, R8 'and R9'> R4, R4 ¹ , R6, R6 ', R5, R5', m, m ', R10, R11, R10', R11 ', W and W ₁ X are as defined in any one of the preceding claims.

21. Process for the preparation of a compound of formula (I) as defined according to any one of the preceding claims comprising the reaction of a compound of formula (II) corresponding:

Wherein R4, R5, R6, R10, R11, W, R4 ', R5, R6', R10 ', R1f, W, X are as defined in formula (I), and a compound of formula (III):

(III) wherein A, a, A ', a' are as defined in formula (I), optionally in the presence of a M. salt.

22. The method of claim 21, wherein, when operating in the absence of a salt of M, is subsequently carried out metallation of the product obtained by action of a salt of M.

23. The method of claim 21 or 22 such that the method according to the invention also comprises the subsequent step of isolating and / or purify the product of formula (I) obtained at the end of this reaction.

24. A process according to any one of claims 20 to 23 such that when m = 0, the compounds of formula (II) are obtained from each of the compounds (V) and (V):

in which R4, R5, R6, W, R4 ', R5 \ R6 \ W are as defined in formula (I), in the presence of compound (IV):

GP _{\ χ} ^ Gp '

(IV) wherein X is defined as in general formula (I) and Gp and Gp 'represent a leaving group.

25. The method of claim 24, such that Gp and Gp 'represent the tosylate group (Gp = Gp' = -OTs).

26. The method of claim 24 or 25 as one operates in the presence of an equivalent of each of the compounds (V) and (V) for one equivalent of the compound of formula (IV).

27. Process according to any one of claims 21 to 23 such that, when m = 1, the compounds of formula (II) are obtained from compounds of formula (VU):

(VII) wherein R4, R5, R6, R10, R11, _W1 R4 ', R5 ^1, R6', R10 ¹ R11 \ W ₁ X are as defined in formula (I) and R "represents a phenol protecting group .

28. Use of a compound of formula (I) according to any one of claims 1 to 19 as a catalyst.

29. Catalyst comprising a compound of formula (I) according to any one of claims 1 to 19.

30. Use of a catalyst according to claim 29 for carrying out a transfer reaction of oxygen, nitrogen or carbon atoms, opening of epoxides, or formation of lactones from ketones, d Epoxidation, asymmetric opening of epoxides or Baeyer-Villiger.

31. An olefin epoxidation process comprising reacting said olefin, an oxidizing agent and a compound of formula (I) as defined in any one of claims 1 to 19.

32. The method of claim 31 further comprising in the reaction mixture a ligand L as defined in any one of claims 1, 7 or 8.

33. The method of claim 31 or 32 wherein M is a group VIIB metal.

34. Process according to any one of claims 31 to 33, such that said oxidizing agent is chosen from NaOCI, PhIO, nBu ₄ NHSO ₅ , mCPBA, H ₂ O ₂ .

35. Composition comprising an olefin, an oxidizing agent and a compound of formula (I), and optionally a ligand, as previously defined according to any one of claims 31 to 34.

36. A method of asymmetric opening of epoxide comprising reacting said epoxide, water and a compound of formula (I) as defined in any one of claims 1 to 19.

37. The method of claim 36 further comprising in the reaction mixture a ligand L as defined in any one of claims 1, 7 or 8.

38. Composition comprising an epoxide, water, a compound of formula (I), and optionally a ligand, as defined according to any one of claims 36 to 37.

39. A Bayer-Villiger process comprising the reaction of a ketone, a peracid and a compound of formula (i) as defined according to any one of claims 1 to 19.

40. The method of claim 39 further comprising in the reaction mixture a ligand L as defined in any one of claims 1, 7 or 8.

41. Composition comprising a ketone, a peracid, a compound of formula (i), and optionally a ligand, as defined according to any one of claims 39 to 40.

42. Process according to claims 36, 37, 39 and 40 such that M is a Group VIIIB metal atom.