A C-H bond activation-based catalytic approach to tetrasubstituted chiral allenes

作者：Wu, Shangze; Huang, Xin; Wu, Wangteng; Li, Pengbin; Fu, Chunling; Ma, Shengming^*

来源：Nature Communications, 2015, 6(1): 7946.

DOI：10.1038/ncomms8946

• ELECTRON-DEFICIENT ARENES
• ASYMMETRIC-SYNTHESIS
• O BOND
• ALLYLATION
• FUNCTIONALIZATION
• ALKYNES

Enantioselective synthesis of fully substituted allenes has been a challenge due to the non-rigid nature of the axial chirality, which spreads over three carbon atoms. Here we show the commercially available simple Rh complex may catalyse the CMD (concerted metalation/deprotonation)-based reaction of the readily available arenes with sterically congested tertiary propargylic carbonates at ambient temperature affording fully substituted allenes. It is confirmed that the excellent designed regioselectivity for the C-C triple bond insertion is induced by the coordination of the carbonyl group in the directing carbonate group as well as the steric effect of the tertiary O-linked carbon atom. When an optically active carbonate was used, surprisingly high efficiency of chirality transfer was realized, affording fully substituted allenes in excellent enantiomeric excess (ee).

• 出版日期2015-8
• 单位浙江大学