Process for producing 2,3-disubstituted-4-substituted cyclopentanones, enantiomorphs, or mixtures thereof
AssigneeTeijin Limited
InventorsRyoji Noyori, Masaaki Suzuki, Toshio Tanaka, Seizi Kurozumi
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Abstract
A process for producing a 2,3-disubstituted-4-substituted cyclopentanone, an enantiomorph thereof, or a mixture of these in an arbitrary ratio. The process comprises (A) subjecting a 4-substituted-2-cyclopentenone, an enantiomorph thereof, or a mixture of these in an arbitrary ratio, and an organocopper compound to conjugate addition-reaction, and thereafter (B) reacting the resulting enolate intermediate with a halide in the presence of a phenyl organotin compound.
Claims18
A process for producing a 2,3-disubstituted-4-substituted cyclopentanone represented by the formula ##STR27## R.sup.2 represents a tri(C.sub.1 -C.sub.7) hydrocarbon silyl group or R.sup.2 O represents an acetal linkage, R.sub.B represents a substituted or unsubstituted C.sub.2 -C.sub.10 alkyl or alkenyl group, Z represents an ethylene, trans-vinylene, or cis-vinylene, group, and R.sub.A represents a substituted or unsubstituted C.sub.1 -C.sub.6 alkyl group, an enantiomorph thereof, or a mixture of these in an arbitrary ratio, which comprises
- (A) subjecting a 4-substituted-2-cyclopentenone represented by the following formula ##STR28## wherein R.sup.2 is as defined above, an enantiomorph thereof, or a mixture of these in an arbitrary ratio, and an organocopper compound formed from an organolithium compound represented by the following formula
- R.sub.B --Li (2)
- wherein R.sub.B is as defined above,
- and a copper compound represented by the following formula
- Cu--Q (3)
- wherein Q represents a halogen atom, a cyano group, a phenylthio group or a 1-pentynyl group, to conjugate addition-reaction, and thereafter,
- (B) reacting the resulting enolate intermediate with a halide represented by the following formula
- X--CH.sub.2 --Z--R.sub.A (5)
- wherein Z and R.sub.A are as defined above, and X represents a halogen atom or a tosyl group, in the presence of an organotin compound represented by the following formula
- R.sub.3 BnY (4)
- wherein R's are identical or different and each represents a phenyl group or a halogen atom provided that two or three R's cannot be halogen atoms at the same time, and Y represents a halogen atom.
A process for producing a 2,3-disubstituted-4-substituted cyclopentanone represented by the formula ##STR30## wherein R.sup.2 represents a tri(C.sub.1 -C.sub.7 -hydrocarbon silyl group or R.sup.2 O represents an acetal linkage, R.sub.B represents a substituted or unsubstituted C.sub.2 -C.sub.10 alkyl or alkenyl group, Z represents an ethylene, transvinylene or cis-vinylene group, and R.sub.A represents a substituted or unsubstituted C.sub.1 -C.sub.6 alkyl group, or --CH.sub.2 --Z--R.sub.A represents --CH.sub.2 --(CH.sub.2).sub.n --COOR.sup.1 wherein R.sup.1 represents a C.sub.1 -C.sub.10 alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted C.sub.3 -C.sub.7 cycloalkyl group or a substituted or unsubstituted phenyl (C.sub.1 -C.sub.2) alkyl group, and n is an integer of 3 to 8,
- an enantiomorph thereof, or a mixture of these in an arbitrary ratio, which comprises
- (A) subjecting a 4-substituted-2-cyclopentanone represented by the following formula ##STR31## wherein R.sup.2 is as defined above, an enantiomorph thereof, or a mixture of these in an arbitrary ratio, and an organocopper compound formed from an organolithium compound represented by the following formula
- R.sub.B --Li (2)
- wherein R.sub.B is as defined above, and a copper compound represented by the following formula
- Cu--Q (3)
- wherein Q represents a halogen atom, a cyano group, a phenylthio group or a 1-pentynyl group, to conjugate addition-reaction, and thereafter,
- (B) reacting the resulting enolate intermediate with a halide represented by the following formula
- X--CH.sub.2 --Z--R.sub.A (5)
- wherein Z and R.sub.A are as defined above, and X represents a halogen atom or a tosyl group, in the presence of an organotin compound represented by the following formula
- R.sub.3 SnY (4)
- wherein R's are identical or different and each represents a phenyl group or a halogen atom provided that two or three R's cannot be halogen atoms at the same time, and Y represents a halogen atom.
A process for producing a 2,3-disubstituted-4-substituted cyclopentanone represented by the formula ##STR32## wherein R.sup.2 represents a tri(C.sub.1 -C.sub.7)-hydrocarbon silyl group or R.sup.2 O represents an acetal linkage, R.sub.B represents a substituted or unsubstituted C.sub.2 -C.sub.10 alkyl or alkenyl group, Z represents an ethynylene, transvinylene or cis-vinylene group, and R.sub.A represents --(CH.sub.2).sub.n-2 COOR.sup.1 wherein .sup.1 represents a C.sub.1 -C.sub.10 alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted C.sub.3 -C.sub.7 cycloalkyl group or a substituted or unsubstituted phenyl (C.sub.1 -C.sub.2) alkyl group, and n is an integer of 3 to 8, an enantiomorph thereof, or a mixture of these in an arbitrary ratio, which comprises
- (A) subjecting a 4-substituted-2-cyclopentanone represented by the following formula ##STR33## wherein R.sup.2 is as defined above, an enantiomorph thereof, or a mixture of these in an arbitrary ratio, and
- an organocopper compound formed from an organolithium compound represented by the following formula
- R.sub.B --Li (2)
- wherein R.sub.B is as defined above, and a copper compound represented by the following formula
- Cu--Q (3)
- wherein Q represents a halogen atom, a cyano group, a phenylthio group or a 1-pentynyl group,
- to conjugate addition-reaction;
- and thereafter,
- (B) reacting the resulting enolate intermediate with a halide represented by the following formula
- X--CH--.sub.2 --Z--R.sub.A (5)
- wherein Z and R.sub.A are as defined above, and X represents a halogen atom or a tosyl group, in the presence of an organotin compound represented by the following formula
- R.sub.3 SnY (4)
- wherein R's are identical or different and each represents a phenyl group or a halogen atom provided that two or three R's cannot be halogen atoms at the same time, and Y represents a halogen atom.
Dependencies are inferred from the claim text.