Process for the asymmetric oxidation of organic compounds with peroxides in the presence of a chiral acid catalyst

A process for the asymmetric oxidation of an organic compound by electrophilic addition of a peroxide compound, said process comprising reacting the organic compound with at least one peroxide compound Rp—OOH in the presence of a chiral catalyst;

• wherein the at least one peroxide compound is activated in favor of said reacting by hydrogen bonding of the at least one peroxide compound to said chiral catalyst;
• wherein said chiral catalyst is selected from the group consisting of chiral compounds (a) and (b), wherein the chiral compounds (a) are selected from the group consisting of chiral imidodiphosphates, and the chiral compounds (b) are selected from the group consisting of phosphoric acids, sulfonic acids, bisulfonimides, triflyl phosphoramides, and phosphinyl phosphoramides, said chiral compounds (b) comprising a catalytically active site [—(P,S)═O][—NHRE, —OH], wherein RE is an electron-withdrawing group;
• wherein the organic compound to be oxidized is selected from the group consisting of xsRXn, Rs1Rs2C═CRs3Rs4 and Rs1Rs2CH—(C═O)Rs3;
• wherein:
• Xs is selected from the group consisting of S, Se, P and N;
• RX is the same or different on X and is selected from the group consisting of (a) —NRY2, (b) —SRY, (c) —ORY, (d) —OSiRy3, (e) C1 to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds, (f) C3-C8-heterocycloalkyl and (g) C6 to C20 aromatic hydrocarbon and partially arene-hydrogenated forms, wherein each of (e)-(g) is optionally substituted by one or more groups selected from the group consisting of (i) C1 to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds, (ii) C3-C8-heterocycloalkyl, and (iii) C6 to C20 aromatic hydrocarbon and partially arene-hydrogenated forms;
• n is 2 when Xs is S or Se;
• or n is 3 when Xs is P or N;
• Rp, RY and Rs1 to Rs4 are independently selected from the group consisting of (a) C1 to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds, (b) C3-C8-heterocycloalkyl and (c) C6 to C20 aromatic hydrocarbon and partially arene-hydrogenated forms, wherein each of (a)-(c) is optionally substituted by one or more groups selected from the group consisting of (i) C1 to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds, (ii) C3-C8-heterocycloalkyl, and (iii) C6 to C20 aromatic hydrocarbon and partially arene-hydrogenated forms;
• or R′ is hydrogen or a radical of the formula:
• wherein aliphatic or aromatic in said formula is selected from the group consisting of (a) C1 to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds, (b) C3-C8-heterocycloalkyl and (c) C6 to C20 aromatic hydrocarbon and partially arene-hydrogenated forms, wherein each of (a)-(c) is optionally substituted by one or more groups selected from the group consisting of (i) C1 to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds, (ii) C3-C8-heterocycloalkyl, and (iii) C6 to C20 aromatic hydrocarbon and partially arene-hydrogenated forms;
• wherein said imidodiphosphates have the formula (I):
• wherein:
• X and Y are, independently from each other, the same or different and represent O, S, Se or NRN;
• Z1 to Z4 are, independently from each other, the same or different and represent O, S or NRN;
• n stands for 0 or 1;
• W is a substituent being capable of forming a covalent or ionic bond with the imidodiphosphate moiety;
• R1 to R4 are, independently from each other, the same or different and are each selected from the group consisting of aliphatic, heteroaliphatic, aromatic and heteroaromatic groups, each of which groups is optionally further substituted by one or more metal-free heterosubstituents, aliphatic, heteroaliphatic, aromatic or heteroaromatic groups, whereby
• R1 and R2 form a ring system with P and, if present, Z1 and Z2, and R3 and R4 form a ring system with P and, if present, Z3 and Z4, respectively;
• and
• RN is selected from the group consisting of (a) hydrogen, (b) C1 to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds, (c) C3-C8-heterocycloalkyl and (d) C6 to C20 aromatic hydrocarbon and partially arene-hydrogenated forms, wherein each of (b)-(d) is optionally substituted by one or more groups selected from the group consisting of (i) C1 to C20 straight chain, branched chain or cyclic aliphatic hydrocarbons, optionally having one or more unsaturated bonds, (ii) C3-C8-heterocycloalkyl, and (iii) C6 to C20 aromatic hydrocarbon and partially arene-hydrogenated forms;
• and tautomeric and ionic forms of said imidodiphosphates.