Ligand‐Controlled Regiodivergence in Nickel‐Catalyzed Vinylcyclopropane Rearrangement

Author:

Irifune Keiichi1,Yamazaki Ken1ORCID,Nakamuro Takayuki2,Murakami Masahiro2,Miura Tomoya1ORCID

Affiliation:

1. Division of Applied Chemistry Okayama University Tsushimanaka, Okayama 700-8530 Japan

2. Department of Synthetic Chemistry and Biological Chemistry Kyoto University Katsura, Kyoto 615-8510 Japan

Abstract

AbstractA ligand‐controlled regiodivergence in Ni‐catalyzed rearrangement of vinylcyclopropanes to 1,4‐ or 1,5‐disubstituted cyclopentenes is reported. The 1,4‐ or 1,5‐disubstituted cyclopentene is selectively obtained depending on the choice of ligands. Detailed kinetic studies and density functional theory calculations on the catalytic cycle revealed that the product selectivity is determined at the reductive elimination step from the six‐membered η1‐allyl intermediate.

Funder

Japan Society for the Promotion of Science

Naito Foundation

Okayama Foundation for Science and Technology

Publisher

Wiley

Subject

General Medicine

Reference70 articles.

1. For reviews on metal-catalyzed regiodivergent reactions see:

2. Regiodivergent Catalysis: A Powerful Tool for Selective Catalysis

3. Metal-catalyzed regiodivergent organic reactions

4. For selected examples on ligand-controlled regiodivergence in nickel-catalyzed reactions see:

5. Ni-Catalyzed Regiodivergent and Stereoselective Hydroalkylation of Acyclic Branched Dienes with Unstabilized C(sp3) Nucleophiles

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