Enantioselective Nickel-Catalyzed Hydrosilylation of 1,1-Disubstituted Allenes

Tao Liu; Xin-Rui Mao; Shuo Song; Zi-Yang Chen; Yichen Wu; Li-Ping Xu; Peng Wang

doi:10.1002/anie.202216878

Enantioselective Nickel-Catalyzed Hydrosilylation of 1,1-Disubstituted Allenes

Angew Chem Int Ed Engl. 2023 Mar 6;62(11):e202216878. doi: 10.1002/anie.202216878. Epub 2023 Feb 7.

Authors

Tao Liu¹, Xin-Rui Mao², Shuo Song¹, Zi-Yang Chen¹, Yichen Wu¹, Li-Ping Xu², Peng Wang^{1

3

4}

Affiliations

¹ State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, CAS, 345 Lingling Road, Shanghai, 200032, P. R. China.
² School of Chemistry and Chemical Engineering, Shandong University of Technology, 266 West Xincun Road, Zibo, 255000, P. R. China.
³ CAS Key Laboratory of Energy Regulation Materials, Shanghai Institute of Organic Chemistry, CAS, 345 Lingling Road, Shanghai, 200032, P. R. China.
⁴ School of Chemistry and Material Sciences, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou, 310024, China.

PMID: 36651564
DOI: 10.1002/anie.202216878

Abstract

Here, we report the first example of Ni-catalyzed asymmetric hydrosilylation of 1,1-disubstituted allenes with high level of regioselectivities and enantioselectivities. The key to achieve this stereoselective hydrosilylation reaction was the development of the SPSiOL-derived bisphosphite ligands (SPSiPO). This protocol features broad substrate scope, excellent functional group, and heterocycle tolerance, thus provides a versatile method for the construction of enantioenriched tertiary allylsilanes in a straightforward and atom-economic manner. DFT calculations were performed to reveal the reaction mechanism and the origins of the enantioselectivity.

Keywords: Allene; Asymmetric Hydrosilylation; Nickel; SPSiPO.

Abstract

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