A1 Journal article (refereed)
Selective Synthesis of Z-Silyl Enol Ethers via Ni-Catalyzed Remote Functionalization of Ketones (2021)


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


JYU authors or editors


Publication details

All authors or editors: Guven, Sinem; Kundu, Gourab; Weßels, Andrea; Ward, Jas S.; Rissanen, Kari; Schoenebeck, Franziska

Journal or series: Journal of the American Chemical Society

ISSN: 0002-7863

eISSN: 1520-5126

Publication year: 2021

Volume: 143

Issue number: 22

Pages range: 8375-8380

Publisher: American Chemical Society (ACS)

Publication country: United States

Publication language: English

DOI: https://doi.org/10.1021/jacs.1c01797

Publication open access: Openly available

Publication channel open access: Partially open access channel

Publication is parallel published (JYX): https://jyx.jyu.fi/handle/123456789/76013


Abstract

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.


Keywords: chemical synthesis; ethers; hydrocarbons; ketones; oligomer; catalysts; nickel

Free keywords: ethers; hydrocarbons; transition metals; ketones; oligomers


Contributing organizations


Ministry reporting: Yes

Reporting Year: 2021

Preliminary JUFO rating: 3


Last updated on 2021-09-08 at 12:06