Stereoselective 1,3-insertions of rhodium(II) azavinyl carbenes

Stepan Chuprakov, Brady T. Worrell, Nicklas Selander, Rakesh K. Sit, Valery V. Fokin

Research output: Contribution to journal › Article

Abstract

Rhodium(II) azavinyl carbenes, conveniently generated from 1-sulfonyl-1,2,3-triazoles, undergo a facile, mild, and convergent formal 1,3-insertion into N-H and O-H bonds of primary and secondary amides, various alcohols, and carboxylic acids to afford a wide range of vicinally bisfunctionalized (Z)-olefins with perfect regio- and stereoselectivity. Utilizing the distinctive functionality installed through these reactions, a number of subsequent rearrangements and cyclizations expand the repertoire of valuable organic building blocks constructed by reactions of transition-metal carbene complexes, including α-allenyl ketones and amino-substituted heterocycles.

Original language	English
Pages (from-to)	195-202
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	136
Issue number	1
DOIs	https://doi.org/10.1021/ja408185c
Publication status	Published - 8 Jan 2014
Externally published	Yes

Fingerprint

ASJC Scopus subject areas

Chemistry(all)
Catalysis
Biochemistry
Colloid and Surface Chemistry

Cite this

Chuprakov, S., Worrell, B. T., Selander, N., Sit, R. K., & Fokin, V. V. (2014). Stereoselective 1,3-insertions of rhodium(II) azavinyl carbenes. Journal of the American Chemical Society, 136(1), 195-202. https://doi.org/10.1021/ja408185c

@article{2d8f323283b842eaa2d33e23453511bc,

title = "Stereoselective 1,3-insertions of rhodium(II) azavinyl carbenes",

abstract = "Rhodium(II) azavinyl carbenes, conveniently generated from 1-sulfonyl-1,2,3-triazoles, undergo a facile, mild, and convergent formal 1,3-insertion into N-H and O-H bonds of primary and secondary amides, various alcohols, and carboxylic acids to afford a wide range of vicinally bisfunctionalized (Z)-olefins with perfect regio- and stereoselectivity. Utilizing the distinctive functionality installed through these reactions, a number of subsequent rearrangements and cyclizations expand the repertoire of valuable organic building blocks constructed by reactions of transition-metal carbene complexes, including α-allenyl ketones and amino-substituted heterocycles.",

author = "Stepan Chuprakov and Worrell, {Brady T.} and Nicklas Selander and Sit, {Rakesh K.} and Fokin, {Valery V.}",

year = "2014",

month = "1",

day = "8",

doi = "10.1021/ja408185c",

language = "English",

volume = "136",

pages = "195--202",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "1",

}

TY - JOUR

T1 - Stereoselective 1,3-insertions of rhodium(II) azavinyl carbenes

AU - Chuprakov, Stepan

AU - Worrell, Brady T.

AU - Selander, Nicklas

AU - Sit, Rakesh K.

AU - Fokin, Valery V.

PY - 2014/1/8

Y1 - 2014/1/8

N2 - Rhodium(II) azavinyl carbenes, conveniently generated from 1-sulfonyl-1,2,3-triazoles, undergo a facile, mild, and convergent formal 1,3-insertion into N-H and O-H bonds of primary and secondary amides, various alcohols, and carboxylic acids to afford a wide range of vicinally bisfunctionalized (Z)-olefins with perfect regio- and stereoselectivity. Utilizing the distinctive functionality installed through these reactions, a number of subsequent rearrangements and cyclizations expand the repertoire of valuable organic building blocks constructed by reactions of transition-metal carbene complexes, including α-allenyl ketones and amino-substituted heterocycles.

AB - Rhodium(II) azavinyl carbenes, conveniently generated from 1-sulfonyl-1,2,3-triazoles, undergo a facile, mild, and convergent formal 1,3-insertion into N-H and O-H bonds of primary and secondary amides, various alcohols, and carboxylic acids to afford a wide range of vicinally bisfunctionalized (Z)-olefins with perfect regio- and stereoselectivity. Utilizing the distinctive functionality installed through these reactions, a number of subsequent rearrangements and cyclizations expand the repertoire of valuable organic building blocks constructed by reactions of transition-metal carbene complexes, including α-allenyl ketones and amino-substituted heterocycles.

UR - http://www.scopus.com/inward/record.url?scp=84892181640&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84892181640&partnerID=8YFLogxK

U2 - 10.1021/ja408185c

DO - 10.1021/ja408185c

M3 - Article

C2 - 24295389

AN - SCOPUS:84892181640

VL - 136

SP - 195

EP - 202

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 1

ER -

Access to Document

10.1021/ja408185c