Nickel-Catalyzed Stereoselective Alkenylation of Ketones Mediated by Hydrazine

Shumei Xia; Dawei Cao; Huiying Zeng; Liang-Nian He; Chao-Jun Li

doi:10.1021/jacsau.2c00320

Nickel-Catalyzed Stereoselective Alkenylation of Ketones Mediated by Hydrazine

JACS Au. 2022 Jul 25;2(8):1929-1934. doi: 10.1021/jacsau.2c00320. eCollection 2022 Aug 22.

Authors

Shumei Xia^{1

2}, Dawei Cao^{1

3}, Huiying Zeng³, Liang-Nian He², Chao-Jun Li¹

Affiliations

¹ Department of Chemistry and FRQNT Centre for Green Chemistry and Catalysis, McGill University, 801 Sherbrooke Street West, Montreal, Quebec H3A 0B8, Canada.
² State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, P. R. China.
³ The State Key Laboratory of Applied Organic Chemistry, Lanzhou University, Lanzhou 730000, P. R. China.

Abstract

The direct conversion of naturally abundant carbonyl compounds provides a powerful platform for the efficient synthesis of valuable chemicals. In particular, the conversion of ketones to alkenes is a commonly encountered chemical transformation, often achieved via the multistep Shapiro reaction with tosylhydrazone and over stoichiometric organolithium or Grignard reagent. Herein, we report an earth abundant nickel-catalyzed alkenylation of naturally abundant methylene ketones to afford a wide range of alkene derivatives, mediated by hydrazine. The protocol features a broad substrate scope (including alkyl ketones, aryl ketones, and aldehydes), good functional group compatibility, mild reaction conditions, water tolerance, and only environmentally friendly N₂, H₂, and H₂O as theoretical byproducts. Moreover, gram-scale synthesis with good yield and generation of pharmaceutical intermediates highlighted its practical applicability.