TY - JOUR
T1 - Ni(I)-Catalyzed β,δ-Vinylarylation of γ,δ-Alkenyl α-Cyanocarboxylic Esters via Contraction of Transient Nickellacycles
AU - Dhungana, Roshan K.
AU - Kc, Shekhar
AU - Basnet, Prakash
AU - Aryal, Vivek
AU - Chesley, Lucas J.
AU - Giri, Ramesh
N1 - Funding Information:
We gratefully acknowledge the NIH NIGMS (No. R35GM133438) and the NSF (No. CHE-1554299) for support of this work. We also thank The Pennsylvania State University and the University of New Mexico (UNM) for additional financial support, and the NSF for upgrades to the NMR (NSF Grant Nos. CHE08-40523 and CHE09-46690) and MS Facilities at UNM. The Bruker X-ray diffractometer was purchased via an NSF CRIF:MU award to UNM (No. CHE04-43580).
Funding Information:
We gratefully acknowledge the NIH NIGMS (No. R35GM133438) and the NSF (No. CHE-1554299) for support of this work. We also thank The Pennsylvania State University and the University of New Mexico (UNM) for additional financial support, and the NSF for upgrades to the NMR (NSF Grant Nos. CHE08-40523 and CHE09-46690) and MS Facilities at UNM. The Bruker X-ray diffractometer was purchased via an NSF CRIF:MU award to UNM (No. CHE04-43580).
Publisher Copyright:
Copyright © 2019 American Chemical Society.
PY - 2019/12/6
Y1 - 2019/12/6
N2 - 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.
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.
UR - https://www.scopus.com/pages/publications/85074701876
UR - https://www.scopus.com/pages/publications/85074701876#tab=citedBy
U2 - 10.1021/acscatal.9b03574
DO - 10.1021/acscatal.9b03574
M3 - Article
AN - SCOPUS:85074701876
SN - 2155-5435
VL - 9
SP - 10887
EP - 10893
JO - ACS Catalysis
JF - ACS Catalysis
IS - 12
ER -