Palladium-catalyzed regio- and enantioselective migratory allylic C(sp3)-H functionalization

Ye-Wei Chen, Yang Liu, Han-Yu Lu, Guo-Qiang Lin () and Zhi-Tao He ()
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Ye-Wei Chen: University of Chinese Academy of Sciences
Yang Liu: University of Chinese Academy of Sciences
Han-Yu Lu: University of Chinese Academy of Sciences
Guo-Qiang Lin: University of Chinese Academy of Sciences
Zhi-Tao He: University of Chinese Academy of Sciences

Nature Communications, 2021, vol. 12, issue 1, 1-9

Abstract: Abstract Transition metal-catalyzed asymmetric allylic substitution with a suitably pre-stored leaving group in the substrate is widely used in organic synthesis. In contrast, the enantioselective allylic C(sp3)-H functionalization is more straightforward but far less explored. Here we report a catalytic protocol for the long-standing challenging enantioselective allylic C(sp3)-H functionalization. Through palladium hydride-catalyzed chain-walking and allylic substitution, allylic C-H functionalization of a wide range of acyclic nonconjugated dienes is achieved in high yields (up to 93% yield), high enantioselectivities (up to 98:2 er), and with 100% atom efficiency. Exploring the reactivity of substrates with varying pKa values uncovers a reasonable scope of nucleophiles and potential factors controlling the reaction. A set of efficient downstream transformations to enantiopure skeletons showcase the practical value of the methodology. Mechanistic experiments corroborate the PdH-catalyzed asymmetric migratory allylic substitution process.

Date: 2021
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DOI: 10.1038/s41467-021-25978-6

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