Patent ID: 7872123

Claim:
A method of performing a catalytic asymmetric O-nitroso Aldol/Michael reaction comprising: reacting a cyclic α,β-unsaturated ketone compound with a nitroso compound in the presence of a proline-based catalyst to provide a heterocyclic product where the cyclic α,β-unsaturated ketone compound has a structure (VII): where: each R 8 may independently represent a substituent selected from the group consisting of hydrogen, halogen, —OR c , —OC(O)R c , —CN, —C(O)R c , —CO 2 R c , —C(O)NR c R d , —NO 2 , —NR c R d , —NR c (O)R d , —NR c CO 2 R d , —NR c S(O) 2 R d , —SR c , —S(O)R c , —S(O) 2 R c , —S(O) 2 NR c R d , C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, C 3-8 cycloalkyl, C 6-10 aryl, 5- to 10-membered heteroaryl, and 3- to 10-membered heterocyclyl; n may be 0, 1, 2, or 3; and each R c and R d may be independently selected from the group consisting of hydrogen, C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, C 3-8 cycloalkyl, C 6-10 aryl, 5- to 10-membered heteroaryl, and 3- to 10-membered heterocyclyl where the nitroso compound has a structure (XI): where: R 14 may represent 1 to 5 substituents each independently selected from the group consisting of hydrogen, halogen, —OR iii , —OC(O)R iii , —CN, —C(O)R iii , —CO 2 R iii , —C(O)R iii R iv , —NO 2 , —NR iii R iv , —NR ii C(O)R iv , —NR iii CO 2 R iv , —NR iii S(O) 2 R iv , —SR iii , —S(O)R iii , —S(O) 2 R iii , —S(O) 2 NR iii R iv , C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, C 3-8 cycloalkyl, C 6-10 aryl, 5- to 10-membered heteroaryl, and 3- to 10-membered heterocyclyl; each R iii and R iv may be independently selected from the group consisting of C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, C 3-8 cycloalkyl, C 6-10 aryl, 5- to 10-membered heteroaryl, and 3- to 10-membered heterocyclyl, where the proline-based catalyst is selected from the group consisting of: where the heterocyclic product has the formula (XV): where: R 14 may represent 1 to 5 substituents each independently selected from the group consisting of hydrogen, halogen, —OR iii , —OC(O)R iii , —CN, —C(O)R iii , —CO 2 R iii , —C(O)NR iii R iv , —NO 2 , —NR iii R iv , —NR ii C(O)R iv , —NR iii CO 2 R iv , —NR iii S(O) 2 R iv , —S(O)R iii , —S(O) 2 R iii , —S(O) 2 NR iii R iv , C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, C 3-8 cycloalkyl, C 6-10 aryl, 5- to 10-membered heteroaryl, and 3- to 10-membered heterocyclyl; each R iii and R iv may be independently selected from the group consisting of C 1-8 alkyl, C 2-8 alkenyl, C 2-8 alkynyl, C 3-8 cycloalkyl, C 6-10 aryl, 5- to 10-membered heteroaryl, and 3- to 10-membered heterocyclyl.