Patent ID: 9050586
Filing Date: 2015-06-09
Classification: B01J,C07B,C07D

Abstract:
1. An enantioselective synthetic method for forming a lactone comprising the step of: reacting an enolisable C wherein the enolisable C wherein, R 9 , R 9′ , R 10 and R 10′ are the same or different and are independently selected from the group consisting of H, halogen, C≡N, NO 2 , C 1 -C 5 haloalkyl, C 1 -C 20 aliphatic, C 1 -C 20 heteroaliphatic, C 3 -C 20 cycloaliphatic, C 2 -C 20 heterocycloaliphatic, C 5 -C 20 aryl, C 3 -C 20 heteroaryl, C(═O)OR 6 , C(═O)NH 2 , C(═O)NHR 6 , C(═O)NR 6 R 7 , OR 6 , OC(═O)R 6 , OC(═O)OR 6 , OC(═O)NH 2 , OC(═O)NHR 6 , OC(═O)NR 6 R 7 , N(H)C(═O)R 6 , N(R 6 )C(═O)R 7 , N(H)C(═O)OR 6 , N(R 6 )C(═O)OR 7 , N(H)C(═O)NH 2 , N(R 6 )C(═O)NH 2 , N(H)C(═O)NHR 6 , N(R 6 )C(═O)NHR 7 , N(H)C(═O)NR 6 R 7 , N(R 6 )C(═O)NR 7 R 8 , S(═O)R 6 , S(═O) 2 R 6 , P(═O)R 6 R 7 , P(═O)(OH)(OH), P(═O)(OH)(OR 6 ), P(═O)(OR 6 )(OR 7 ); or R 9 and R 10 together with the carbon atoms to which they are attached define a C 3 -C 20 cycloaliphatic ring, a C 2 -C 20 heterocycloaliphatic ring, a C 5 -C 20 aryl ring, or a C 3 -C 20 heteroaryl ring; or R 9′ and R 10′ together with the carbon atoms to which they are attached define a C 3 -C 20 cycloaliphatic ring, or a C 2 -C 20 heterocycloaliphatic ring subject to the proviso that at least one of the carbon atoms to which R 9′ and R 10′ are attached is saturated; R 6 , R 7 and R 8 are the same or different and are independently selected from the group consisting of C 1 -C 20 aliphatic, C 1 -C 20 heteroaliphatic, C 3 -C 20 cycloaliphatic, C 2 -C 20 heterocycloaliphatic, C 5 -C 20 aryl, C 3 -C 20 heteroaryl, and combinations thereof; n is 1-5; and wherein the bifunctional organocatalyst is selected from the group consisting of: wherein E is a moiety selected from the group consisting of: X is O or S; M is selected from the group consisting of H, OH, SH, O(C 1 -C 5 aliphatic), and S(C 1 -C 5 aliphatic); Z is C 1 -C 5 aliphatic optionally substituted one or more times with at least one of a halogen, cyano, CF 3 , NO 2 , C 1 -C 5 ketone, C 1 -C 5 ester, C 1 -C 10 amide, C 1 -C 5 sulfone, C 1 -C 5 sulfoxide and combinations thereof; B is selected from the group consisting of C 1 -C 20 aliphatic, C 1 -C 20 heteroaliphatic, C 3 -C 20 cycloaliphatic, C 2 -C 20 heterocycloaliphatic, C 5 -C 20 aryl, C 3 -C 20 heteroaryl, and combinations thereof optionally substituted one or more times with at least one of a halogen, cyano, CF 3 , NO 2 , C 1 -C 5 ketone, C 1 -C 5 ester, C 1 -C 10 amide, C 1 -C 5 sulfone, C 1 -C 5 sulfoxide, C 1 -C 5 alkyl and combinations thereof; R 17 and R 18 are the same or different and are independently selected from the group consisting of H, C 3 -C 10 branched aliphatic, C 3 -C 10 branched heteroaliphatic, C 3 -C 20 cycloaliphatic, C 2 -C 20 heterocycloaliphatic, C 5 -C 20 aryl, C 3 -C 20 heteroaryl, Br, I and combinations thereof; or R 17 and R 18 together with the carbon atoms to which they are attached define a monocyclic or polycyclic structure selected from the group consisting of C 3 -C 20 cycloaliphatic, C 2 -C 20 heterocycloaliphatic, C 5 -C 20 aryl, C 3 -C 20 heteroaryl; R 13 and R 14 are the same or different and are independently selected from the group consisting of C 1 -C 20 aliphatic, C 1 -C 20 heteroaliphatic, C 3 -C 20 cycloaliphatic, C 2 -C 20 heterocycloaliphatic, C 5 -C 20 aryl, C 3 -C 20 heteroaryl, and combinations thereof optionally substituted one or more times with at least one of a halogen, cyano, CF 3 , NO 2 , C 1 -C 5 ketone, C 1 -C 5 ester, C 1 -C 10 amide, C 1 -C 5 sulfone, C 1 -C 5 sulfoxide, C 1 -C 5 alkyl and combinations thereof; or R 13 and R 14 together with the carbon atom to which they are attached define a C 3 -C 20 cycloaliphatic ring, C 2 -C 20 heterocycloaliphatic ring, C 5 -C 20 aryl ring, C 3 -C 20 heteroaryl ring optionally substituted one or more times with at least one of a halogen, cyano, CF 3 , NO 2 , C 1 -C 5 ketone, C 1 -C 5 ester, C 1 -C 10 amide, C 1 -C 5 sulfone, C 1 -C 5 sulfoxide, C 1 -C 5 alkyl and combinations thereof.