Direct Asymmetric Allylic Alkenylation of N-Itaconimides with Morita–Baylis–Hillman Carbonates

Wenguo Yang, Davin Tan, Lixin Li, Zhiqiang Han, Lin Yan, Kuo-Wei Huang, Choon-Hong Tan and Zhiyong Jiang

J. Org. Chem.201277156600-6607

Abstract: The asymmetric allylic alkenylation of Morita–Baylis–Hillman (MBH) carbonates with N-itaconimides as nucleophiles has been developed using a commercially available Cinchona alkaloid catalyst. A variety of multifunctional chiral α-methylene-β-maleimide esters were attained in moderate to excellent yields (up to 99%) and good to excellent enantioselectivities (up to 91% ee). The origin of the regio- and stereoselectivity was verified by DFT methods. Calculated geometries and relative energies of various transition states strongly support the observed regio- and enantioselectivity.

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