Abstract
The compatibility between photogenerated silyl radicals and transition metal catalysis remains one of the foremost challenges in modern synthetic organic chemistry. Herein, we present the cooperation of photoredox/nickel catalyzed allylic silylation of diverse allyl acetates (even with multiple alkenyl groups) via a silyl radical intermediate. This protocol successfully surmounts the long-standing challenge and provides straightforward, modular synthetic access to substituted allylsilanes from silanecarboxylic acids. Moreover, this strategy has advantages of green and mild conditions over established nucleophilic substitution methods via a silanion pathway. Mechanistic study shows that the formation of silyl radical initiated by photo-induced decarboxylation of silanecarboxylic acids, and the nickel-catalyzed oxidative addition of allyl acetate, followed by silyl radical addition are critical processes. DFT computation reveals that the regioselectivity is controlled by the silyl radical attack of the sterically less hindered or less substituted terminal allylic carbon atom.
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Disclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.