Catalytic Asymmetric Conjugate Addition of 2-Methyl-3,5-dinitrobenzoates to Unsaturated Ketones.

ABSTRACT

Asymmetric catalytic vinylogous Michael addition of 2-methyl-3,5-dinitrobenzoates to unsaturated ketones catalyzed by chiral rhodium catalysts has been established. This strategy allowed the synthesis of a variety of optically pure compounds containing imidazole and 3,5-dinitrobenzene skeletons in 64-98% yields with 88-98% ee. The developed reaction not only represents highly asymmetric catalytic enantioselective vinylogous Michael addition employing 2-methyl-3,5-dinitrobenzoates as a building block but also enriches the chemistry of catalytic asymmetric vinylogous Michael addition of 2-methyl-3,5-dinitrobenzoates. Furthermore, the protocol showed obvious advantages in reaction activity and enantioselectivity. When the chiral rhodium catalyst was reduced to 0.06 mol %, the gram-level reaction was still achieved to provide the desired product with 95% ee.