Copper-mediated oxidative transformation of N-allyl enamine carboxylates toward synthesis of azaheterocycles

Kah Kah Toh; Anup Biswas; Yi Feng Wang; Yun Yun Tan; Shunsuke Chiba

doi:10.1021/ja500382c

Copper-mediated oxidative transformation of N-allyl enamine carboxylates toward synthesis of azaheterocycles

Kah Kah Toh, Anup Biswas, Yi Feng Wang, Yun Yun Tan, Shunsuke Chiba^*

^*Corresponding author for this work

Nanyang Technological University

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

85 Citations (Scopus)

Abstract

A method for synthesis of 3-azabicyclo[3.1.0]hex-2-enes has been developed by intramolecular cyclopropanation of readily available N-allyl enamine carboxylates. Two complementary reaction conditions, CuBr-mediated aerobic and CuBr₂-catalyzed-PhIO₂-mediated systems effectively induced stepwise cyclopropanation via carbocupration of alkenes. Oxidative cyclopropane ring-opening of 5-substituted 3-azabicyclo[3.1.0]hex-2-enes was also developed for synthesis of highly substituted pyridines. In addition, diastereoselective reduction of 3-azabicyclo[3.1.0]hex-2-enes to 3-azabicyclo[3.1.0]hexanes was achieved using NaBH₃CN in the presence of acetic acid.

Original language	English
Pages (from-to)	6011-6020
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	136
Issue number	16
DOIs	https://doi.org/10.1021/ja500382c
Publication status	Published - Apr 23 2014
Externally published	Yes

ASJC Scopus Subject Areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

Access to Document

10.1021/ja500382c

Cite this

@article{e878af6b1eac4bb2b91caed14d4c5c8d,

title = "Copper-mediated oxidative transformation of N-allyl enamine carboxylates toward synthesis of azaheterocycles",

abstract = "A method for synthesis of 3-azabicyclo[3.1.0]hex-2-enes has been developed by intramolecular cyclopropanation of readily available N-allyl enamine carboxylates. Two complementary reaction conditions, CuBr-mediated aerobic and CuBr2-catalyzed-PhIO2-mediated systems effectively induced stepwise cyclopropanation via carbocupration of alkenes. Oxidative cyclopropane ring-opening of 5-substituted 3-azabicyclo[3.1.0]hex-2-enes was also developed for synthesis of highly substituted pyridines. In addition, diastereoselective reduction of 3-azabicyclo[3.1.0]hex-2-enes to 3-azabicyclo[3.1.0]hexanes was achieved using NaBH3CN in the presence of acetic acid.",

author = "Toh, \{Kah Kah\} and Anup Biswas and Wang, \{Yi Feng\} and Tan, \{Yun Yun\} and Shunsuke Chiba",

year = "2014",

month = apr,

day = "23",

doi = "10.1021/ja500382c",

language = "English",

volume = "136",

pages = "6011--6020",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "16",

}

TY - JOUR

T1 - Copper-mediated oxidative transformation of N-allyl enamine carboxylates toward synthesis of azaheterocycles

AU - Toh, Kah Kah

AU - Biswas, Anup

AU - Wang, Yi Feng

AU - Tan, Yun Yun

AU - Chiba, Shunsuke

PY - 2014/4/23

Y1 - 2014/4/23

N2 - A method for synthesis of 3-azabicyclo[3.1.0]hex-2-enes has been developed by intramolecular cyclopropanation of readily available N-allyl enamine carboxylates. Two complementary reaction conditions, CuBr-mediated aerobic and CuBr2-catalyzed-PhIO2-mediated systems effectively induced stepwise cyclopropanation via carbocupration of alkenes. Oxidative cyclopropane ring-opening of 5-substituted 3-azabicyclo[3.1.0]hex-2-enes was also developed for synthesis of highly substituted pyridines. In addition, diastereoselective reduction of 3-azabicyclo[3.1.0]hex-2-enes to 3-azabicyclo[3.1.0]hexanes was achieved using NaBH3CN in the presence of acetic acid.

AB - A method for synthesis of 3-azabicyclo[3.1.0]hex-2-enes has been developed by intramolecular cyclopropanation of readily available N-allyl enamine carboxylates. Two complementary reaction conditions, CuBr-mediated aerobic and CuBr2-catalyzed-PhIO2-mediated systems effectively induced stepwise cyclopropanation via carbocupration of alkenes. Oxidative cyclopropane ring-opening of 5-substituted 3-azabicyclo[3.1.0]hex-2-enes was also developed for synthesis of highly substituted pyridines. In addition, diastereoselective reduction of 3-azabicyclo[3.1.0]hex-2-enes to 3-azabicyclo[3.1.0]hexanes was achieved using NaBH3CN in the presence of acetic acid.

UR - http://www.scopus.com/inward/record.url?scp=84899583974&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84899583974&partnerID=8YFLogxK

U2 - 10.1021/ja500382c

DO - 10.1021/ja500382c

M3 - Article

C2 - 24730391

AN - SCOPUS:84899583974

SN - 0002-7863

VL - 136

SP - 6011

EP - 6020

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 16

ER -

Copper-mediated oxidative transformation of N-allyl enamine carboxylates toward synthesis of azaheterocycles

Abstract

ASJC Scopus Subject Areas

Access to Document

Other files and links

Fingerprint

Cite this