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Enantioselective Intramolecular [2,3]-Sigmatropic Rearrangement of Aldehydes via a Sulfonium Enamine Intermediate |
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| Authors: | Dr Li Li Baoli Chen Prof Dr Jiean Chen Prof Dr Yong Huang |
| Institution: | 1. Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR, China;2. Pingshan Translational Medicine Center, Shenzhen Bay Laboratory, Shenzhen, 518055 China
Shenzhen Public Platform of Drug Screening and Preclinical Evaluation, Peking University Shenzhen Graduate School, Shenzhen, 518055 China;3. Pingshan Translational Medicine Center, Shenzhen Bay Laboratory, Shenzhen, 518055 China |
| Abstract: | The rearrangement of sulfur-containing aldehydes by using a sulfonium enamine intermediate as a formylcarbene mimetic is reported. This is an enantioselective, organocatalytic 2,3]-sigmatropic rearrangement enabling chiral cyclic sulfides bearing an α-quaternary chiral center to be prepared in high optical purity. The enantioselectivity is controlled with a cooperative organocatalyst pair consisting of a chiral amine and a chiral phosphoric acid (CPA). The synthetic versatility of this method is demonstrated by its rapid access to structurally diverse chiral spiro S-heterocycles. |
| Keywords: | [2 3]-rearrangement reactions carbenes chiral sulfides sulfonium ylides synergistic organocatalysis |