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

作者：Yang, Wenguo; Tan, Davin; Li, Lixin; Han, Zhiqiang; Yan, Lin; Huang, Kuo-Wei^*; Tan, Choon-Hong; Jiang, Zhiyong

来源：Journal of Organic Chemistry, 2012, 77(15): 6600-6607.

DOI：10.1021/jo3012539

• CHIRAL BICYCLIC GUANIDINE
• CATALYZED ENANTIOSELECTIVE REACTIONS
• 3-SUBSTITUTED BENZOFURAN-2(3H)-ONES
• CONJUGATE ADDITION
• 3+2 ANNULATION
• ALKYLATION
• CONSTRUCTION
• QUATERNARY
• SUBSTITUTION
• TRIFLUOROMETHYLATION

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 amethylene-beta-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.

• 出版日期2012-8-3
• 单位河南大学; KAUST; 南阳理工学院