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

Bijay Shrestha; Prakash Basnet; Roshan K. Dhungana; Shekhar Kc; Surendra Thapa; Jeremiah M. Sears; Ramesh Giri

doi:10.1021/jacs.7b06340

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

Bijay Shrestha, Prakash Basnet, Roshan K. Dhungana, Shekhar Kc, Surendra Thapa, Jeremiah M. Sears, Ramesh Giri

Chemistry

Research output: Contribution to journal › Article › peer-review

184 Scopus citations

Abstract

We disclose a strategy for Ni-catalyzed dicarbofunctionalization of olefins in styrenes 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 carbometalation 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-triarylethyl products that occur as structural motifs in various natural products.

Original language	English (US)
Pages (from-to)	10653-10656
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	139
Issue number	31
DOIs	https://doi.org/10.1021/jacs.7b06340
State	Published - Aug 9 2017

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/jacs.7b06340

Cite this

@article{43c8a557ad6543169e2b1249c2ab3fa6,

title = "Ni-Catalyzed Regioselective 1,2-Dicarbofunctionalization of Olefins by Intercepting Heck Intermediates as Imine-Stabilized Transient Metallacycles",

abstract = "We disclose a strategy for Ni-catalyzed dicarbofunctionalization of olefins in styrenes 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 carbometalation 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-triarylethyl products that occur as structural motifs in various natural products.",

author = "Bijay Shrestha and Prakash Basnet and Dhungana, {Roshan K.} and Shekhar Kc and Surendra Thapa and Sears, {Jeremiah M.} and Ramesh Giri",

note = "Funding Information: We thank the University of New Mexico (UNM) and the National Science Foundation (NSF CHE-1554299) for financial support, and upgrades to the NMR (NSF Grants CHE08-40523 and CHE09-46690) and MS Facilities. The Bruker X-ray diffractometer was purchased via an NSF CRIF:MU award to UNM (CHE04-43580). Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = aug,

day = "9",

doi = "10.1021/jacs.7b06340",

language = "English (US)",

volume = "139",

pages = "10653--10656",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "31",

}

Ni-Catalyzed Regioselective 1,2-Dicarbofunctionalization of Olefins by Intercepting Heck Intermediates as Imine-Stabilized Transient Metallacycles. / Shrestha, Bijay; Basnet, Prakash; Dhungana, Roshan K. et al.
In: Journal of the American Chemical Society, Vol. 139, No. 31, 09.08.2017, p. 10653-10656.

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - Ni-Catalyzed Regioselective 1,2-Dicarbofunctionalization of Olefins by Intercepting Heck Intermediates as Imine-Stabilized Transient Metallacycles

AU - Shrestha, Bijay

AU - Basnet, Prakash

AU - Dhungana, Roshan K.

AU - Kc, Shekhar

AU - Thapa, Surendra

AU - Sears, Jeremiah M.

AU - Giri, Ramesh

N1 - Funding Information: We thank the University of New Mexico (UNM) and the National Science Foundation (NSF CHE-1554299) for financial support, and upgrades to the NMR (NSF Grants CHE08-40523 and CHE09-46690) and MS Facilities. The Bruker X-ray diffractometer was purchased via an NSF CRIF:MU award to UNM (CHE04-43580). Publisher Copyright: © 2017 American Chemical Society.

PY - 2017/8/9

Y1 - 2017/8/9

N2 - We disclose a strategy for Ni-catalyzed dicarbofunctionalization of olefins in styrenes 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 carbometalation 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-triarylethyl products that occur as structural motifs in various natural products.

AB - We disclose a strategy for Ni-catalyzed dicarbofunctionalization of olefins in styrenes 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 carbometalation 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-triarylethyl products that occur as structural motifs in various natural products.

UR - http://www.scopus.com/inward/record.url?scp=85027131744&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85027131744&partnerID=8YFLogxK

U2 - 10.1021/jacs.7b06340

DO - 10.1021/jacs.7b06340

M3 - Article

C2 - 28737904

AN - SCOPUS:85027131744

SN - 0002-7863

VL - 139

SP - 10653

EP - 10656

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 31

ER -

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

Abstract

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this