Selective Synthesis of Z-Silyl Enol Ethers via Ni-Catalyzed Remote Functionalization of Ketones
Guven, S., Kundu, G., Weßels, A., Ward, J. S., Rissanen, K., & Schoenebeck, F. (2021). Selective Synthesis of Z-Silyl Enol Ethers via Ni-Catalyzed Remote Functionalization of Ketones. Journal of the American Chemical Society, 143(22), 8375-8380. https://doi.org/10.1021/jacs.1c01797
Published inJournal of the American Chemical Society
© 2021 The Authors. Published by American Chemical Society
We report a remote functionalization strategy, which allows the Z-selective synthesis of silyl enol ethers of (hetero)aromatic and aliphatic ketones via Ni-catalyzed chain walking from a distant olefin site. The positional selectivity is controlled by the directionality of the chain walk and is independent of thermodynamic preferences of the resulting silyl enol ether. Our mechanistic data indicate that a Ni(I) dimer is formed under these conditions, which serves as a catalyst resting state and, upon reaction with an alkyl bromide, is converted to [Ni(II)-H] as an active chain-walking/functionalization catalyst, ultimately generating a stabilized η3-bound Ni(II) enolate as the key selectivity-controlling intermediate.
PublisherAmerican Chemical Society (ACS)
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Additional information about fundingF.S. acknowledges the RWTH Aachen University and the European Research Council (ERC-864849) for funding. K.R. acknowledges the Alexander von Humboldt Foundation (for the AvH Research Award) and J.S.W. the Finnish Cultural Foundation Central Fund (grant number 00201148) for financial support. Calculations were performed with computing resources granted by JARA-HPC from RWTH Aachen University under project “jara0091”. ...
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