Ni(I)-Catalyzed β,δ-Vinylarylation of γ,δ-Alkenyl α-Cyanocarboxylic Esters via Contraction of Transient Nickellacycles

Roshan K. Dhungana, Shekhar Kc, Prakash Basnet, Vivek Aryal, Lucas J. Chesley, Ramesh Giri

Research output: Contribution to journalArticlepeer-review

6 Scopus citations

Abstract

We disclose a transmetalation-initiated Ni(I)-catalyzed regioselective β,δ-vinylarylation of γ,δ-alkenyl α-cyanocarboxylic esters with vinyl triflates and arylzinc reagents. This reaction proceeds via contraction of six-membered nickellacycles to five-membered nickellacycles to form carbon-carbon bonds at the nonclassical homovicinal sites, and it provides expeditious access to a wide range of complex aliphatic α-cyanoesters, α-cyanocarboxylic acids, dicarboxylic acids, dicarboxylic acid monoamides, monocarboxylic acids, nitriles, and spirolactones. Control, deuterium labeling, and crossover experiments indicate that (i) the nickellacycle contraction occurs by β-H elimination, followed by hydronickellation on transiently formed alkenes, and (ii) the Ni species are stabilized as Ni-enolates.

Original languageEnglish (US)
Pages (from-to)10887-10893
Number of pages7
JournalACS Catalysis
Volume9
Issue number12
DOIs
StatePublished - Dec 6 2019

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

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