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 journalArticle

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

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Dicarboxylic Acids
Esters
Carbon
Nitriles
Spironolactone
Acids
Deuterium
Alkenes
Labeling
Olefins
Experiments
vinyl triflate

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Cite this

Dhungana, Roshan K. ; Kc, Shekhar ; Basnet, Prakash ; Aryal, Vivek ; Chesley, Lucas J. ; Giri, Ramesh. / Ni(I)-Catalyzed β,δ-Vinylarylation of γ,δ-Alkenyl α-Cyanocarboxylic Esters via Contraction of Transient Nickellacycles. In: ACS Catalysis. 2019 ; Vol. 9, No. 12. pp. 10887-10893.
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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.",
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Ni(I)-Catalyzed β,δ-Vinylarylation of γ,δ-Alkenyl α-Cyanocarboxylic Esters via Contraction of Transient Nickellacycles. / Dhungana, Roshan K.; Kc, Shekhar; Basnet, Prakash; Aryal, Vivek; Chesley, Lucas J.; Giri, Ramesh.

In: ACS Catalysis, Vol. 9, No. 12, 06.12.2019, p. 10887-10893.

Research output: Contribution to journalArticle

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AU - Giri, Ramesh

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AB - 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.

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