Gold(I)‐Catalyzed Highly Diastereo‐ and Enantioselective Alkyne Oxidation/Cyclopropanation of 1,6‐Enynes |
| |
| Authors: | Deyun Qian Haoxiang Hu Feng Liu Bin Tang Weimin Ye Yidong Wang Prof Junliang Zhang |
| |
| Institution: | Shanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal University, Shanghai 200062 (P.R. China) |
| |
| Abstract: | A highly enantioselective oxidative cyclopropanation of 1,6‐enynes catalyzed by cationic AuI/chiral phophoramidite complexes is presented. The new method provides convenient access to densely functionalized bicyclo3.1.0]hexanes bearing three contiguous quaternary and tertiary stereogenic centers with high enantioselectivity (up to e.r. 98:2). Control experiments suggest that the quinoline moiety of the β‐gold vinyloxyquinolinium intermediate in the reaction plays an important role in promoting good enantioselectivity through a transitional auxiliary effect in the transition state. |
| |
| Keywords: | alkyne oxidation carbenoids cyclopropanation enantioselectivity gold |
|
