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Title: Ni-Catalyzed Regioselective 1,2-Dicarbofunctionalization of Olefins by Intercepting Heck Intermediates as Imine-Stabilized Transient Metallacycles

We disclose a strategy for Ni-catalyzed regioselective dicarbofunctionalization of olefins in styrene derivatives by intercepting Heck C(sp 3)-NiX intermediates with arylzinc reagents. This approach utilizes a readily removable imine as a coordinating group that plays a dual role of intercepting oxidative addition species derived from aryl halides and triflates to promote Heck carbometallation, and stabilizing the Heck C(sp 3)-NiX intermediates as transient metallacycles to suppress β-hydride elimination and facilitate transmetalation/reductive elimination steps. This method affords diversely-substituted 1,1,2-riarylethyl products that occur as structural motifs in various natural products.
Authors:
 [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [2] ; ORCiD logo [1]
  1. Univ. of New Mexico, Albuquerque, NM (United States)
  2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Report Number(s):
SAND-2017-7180J
Journal ID: ISSN 0002-7863; 655131
Grant/Contract Number:
AC04-94AL85000
Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 139; Journal Issue: 31; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Research Org:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org:
USDOE National Nuclear Security Administration (NNSA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1399511

Shrestha, Bijay, Basnet, Prakash, Dhungana, Roshan K., KC, Shekhar, Thapa, Surendra, Sears, Jeremiah M., and Giri, Ramesh. Ni-Catalyzed Regioselective 1,2-Dicarbofunctionalization of Olefins by Intercepting Heck Intermediates as Imine-Stabilized Transient Metallacycles. United States: N. p., Web. doi:10.1021/jacs.7b06340.
Shrestha, Bijay, Basnet, Prakash, Dhungana, Roshan K., KC, Shekhar, Thapa, Surendra, Sears, Jeremiah M., & Giri, Ramesh. Ni-Catalyzed Regioselective 1,2-Dicarbofunctionalization of Olefins by Intercepting Heck Intermediates as Imine-Stabilized Transient Metallacycles. United States. doi:10.1021/jacs.7b06340.
Shrestha, Bijay, Basnet, Prakash, Dhungana, Roshan K., KC, Shekhar, Thapa, Surendra, Sears, Jeremiah M., and Giri, Ramesh. 2017. "Ni-Catalyzed Regioselective 1,2-Dicarbofunctionalization of Olefins by Intercepting Heck Intermediates as Imine-Stabilized Transient Metallacycles". United States. doi:10.1021/jacs.7b06340. https://www.osti.gov/servlets/purl/1399511.
@article{osti_1399511,
title = {Ni-Catalyzed Regioselective 1,2-Dicarbofunctionalization of Olefins by Intercepting Heck Intermediates as Imine-Stabilized Transient Metallacycles},
author = {Shrestha, Bijay and Basnet, Prakash and Dhungana, Roshan K. and KC, Shekhar and Thapa, Surendra and Sears, Jeremiah M. and Giri, Ramesh},
abstractNote = {We disclose a strategy for Ni-catalyzed regioselective dicarbofunctionalization of olefins in styrene derivatives by intercepting Heck C(sp3)-NiX intermediates with arylzinc reagents. This approach utilizes a readily removable imine as a coordinating group that plays a dual role of intercepting oxidative addition species derived from aryl halides and triflates to promote Heck carbometallation, and stabilizing the Heck C(sp3)-NiX intermediates as transient metallacycles to suppress β-hydride elimination and facilitate transmetalation/reductive elimination steps. This method affords diversely-substituted 1,1,2-riarylethyl products that occur as structural motifs in various natural products.},
doi = {10.1021/jacs.7b06340},
journal = {Journal of the American Chemical Society},
number = 31,
volume = 139,
place = {United States},
year = {2017},
month = {7}
}