Direct asymmetric allylic alkenylation of N-itaconimides with Morita–Baylis–Hillman carbonates

• Main Authors: Yang, Wenguo, Tan, Davin, Li, Lixin, Han, Zhiqiang, Yan, Lin, Huang, Kuo-Wei, Tan, Choon-Hong, Jiang, Zhiyong
• Other Authors: School of Physical and Mathematical Sciences
• Format: Article
• Language: English
• Published: 2013
• Online Access: https://hdl.handle.net/10356/98322; http://hdl.handle.net/10220/17040
• Institution: Nanyang Technological University

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.