Nickel-catalysed regio- and stereoselective hydrocyanation of alkynoates and its mechanistic insights proposed by DFT calculations

Shigeru Arai; Koichi Nakazawa; Xiao-Fei Yang; Masaya Nakajima; Shinji Harada; Atsushi Nishida

doi:10.1039/d4ob00380b

Nickel-catalysed regio- and stereoselective hydrocyanation of alkynoates and its mechanistic insights proposed by DFT calculations

Org Biomol Chem. 2024 May 8;22(18):3606-3610. doi: 10.1039/d4ob00380b.

Authors

Shigeru Arai^{1

2}, Koichi Nakazawa¹, Xiao-Fei Yang¹, Masaya Nakajima^{1

3}, Shinji Harada^{1

2

4}, Atsushi Nishida¹

Affiliations

¹ Graduate School of Pharmaceutical Sciences, Chiba University, 1-8-1 Inohana, Chuo-ku, Chiba, 260-8675, Japan. araisgr@chiba-u.jp.
² Molecular Chirality Research Center, Chiba University, 1-33, Yayoi-cho, Inage-ku, Chiba, 263-8522, Japan.
³ Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
⁴ Institute for Advanced Academic Research, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan.

PMID: 38629974
DOI: 10.1039/d4ob00380b

Abstract

We have developed a nickel-catalysed regio- and stereoselective hydrocyanation of alkynoates that gives syn-β-cyanoalkenes. DFT calculations suggest that a favored transition state promotes Cα-H bond formation for determining regio- and stereoselectivity of the products.