title: Enantioselective construction of branched 1,3-dienyl substituted quaternary carbon stereocenters by asymmetric allenyl Claisen rearrangement.
abstract: The availability of enantiomerically enriched 1,3-dienyl substituted quaternary stereocenters is highly valuable for the synthesis of complex natural compounds. Despite great advances in the area of construction of alkenyl-substituted types, a general, practical catalytic system that works for enantioselective formation of 1,3-diene derivatives still remains to be developed. Herein, we disclose the first asymmetric Claisen rearrangement of allenyl vinyl ethers to access optically active β-ketoesters, containing branched 1,3-butadienyl substituted stereocenters. A variety of substrates bearing a range of useful functional groups were well tolerated, thus affording the corresponding products with excellent enantioselectivities (up to 99% ee) and high yields (up to 91%).
authors.affiliation: Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, China. liuxh@scu.edu.cn xmfeng@scu.edu.cn.
authors.forename: Yangbin
authors.initials: Y
authors.lastname: Liu
authors.affiliation: Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, China. liuxh@scu.edu.cn xmfeng@scu.edu.cn.
authors.forename: Haipeng
authors.initials: H
authors.lastname: Hu
authors.affiliation: Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, China. liuxh@scu.edu.cn xmfeng@scu.edu.cn.
authors.forename: Lili
authors.initials: L
authors.lastname: Lin
authors.affiliation: Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, China. liuxh@scu.edu.cn xmfeng@scu.edu.cn.
authors.forename: Xiaoyu
authors.initials: X
authors.lastname: Hao
authors.affiliation: Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, China. liuxh@scu.edu.cn xmfeng@scu.edu.cn.
authors.forename: Xiaohua
authors.initials: X
authors.lastname: Liu
authors.affiliation: Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, China. liuxh@scu.edu.cn xmfeng@scu.edu.cn and Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), China.
authors.forename: Xiaoming
authors.initials: X
authors.lastname: Feng