Palladium-Catalyzed Ring Opening of Vinyl Oxetanes Enables Asymmetric Dearomative [6 + 2] Cycloaddition of
Yan Chen1, Xin-Hua Zhang1, Zhen-Hua Wang1
1Innovation Research Center of Chiral Drugs, Institute for Advanced Study, Chengdu University, Chengdu 610106, China.
Abstract:
We present a catalyst system consisting of a chiral (R)-xyl-BINAP ligand and PdCl2, which enables the ring opening of vinyl oxetanes to drive asymmetric dearomatization of 3-nitroindoles for the enantioselective [6 + 2] cycloaddition, leading to the construction of indoline-fused oxa-eight-membered rings in good yields with high to excellent stereoselectivities (up to 96% yield, >95:5 dr, and 98% ee). This work represents the first example of asymmetric dearomatization of electron-deficient nitroindoles triggered by oxa-π-allylpalladium 1,6-dipoles.
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