Copper-promoted site-selective carbonylation of sp(3) and sp(2) C-H
bonds with nitromethane

Xuesong Wu; Jinmin Miao; Yanrong Li; Guigen Li; Haibo Ge

doi:10.1039/c6sc01087c

Copper-promoted site-selective carbonylation of sp(3) and sp(2) C-H bonds with nitromethane

Xuesong Wu, Jinmin Miao, Yanrong Li, Guigen Li, Haibo Ge

Chemistry and Biochemistry

Research output: Contribution to journal › Article

37 Scopus citations

Abstract

Copper-promoted direct carbonylation of unactivated sp(3)C-H and aromatic sp(2)C-H bonds of amides was developed using nitromethane as a novel carbonyl source. The sp(3)C-H functionalization showed high site-selectivity by favoring the C-H bonds of alpha-methyl groups. The sp(2)C-H carbonylation featured high regioselectivity and good functional group compatibility. Kinetic isotope effect studies indicated that the sp(3)C-H bond breaking step is reversible, whereas the sp(2)C-H bond cleavage is an irreversible but not the rate-determining step. Control experiments showed that a nitromethyl intermediate should be involved in the present reaction.

Original language	English
Pages (from-to)	5260-5264
Number of pages	5
Journal	Chemical Science
Volume	7
Issue number	8
DOIs	https://doi.org/10.1039/c6sc01087c
State	Published - 2016

Access to Document

10.1039/c6sc01087c

Cite this

@article{bc972db6875f48a18f4636dd971804aa,

title = "Copper-promoted site-selective carbonylation of sp(3) and sp(2) C-H bonds with nitromethane",

abstract = "Copper-promoted direct carbonylation of unactivated sp(3)C-H and aromatic sp(2)C-H bonds of amides was developed using nitromethane as a novel carbonyl source. The sp(3)C-H functionalization showed high site-selectivity by favoring the C-H bonds of alpha-methyl groups. The sp(2)C-H carbonylation featured high regioselectivity and good functional group compatibility. Kinetic isotope effect studies indicated that the sp(3)C-H bond breaking step is reversible, whereas the sp(2)C-H bond cleavage is an irreversible but not the rate-determining step. Control experiments showed that a nitromethyl intermediate should be involved in the present reaction.",

author = "Xuesong Wu and Jinmin Miao and Yanrong Li and Guigen Li and Haibo Ge",

note = "Funding Information: Financial support from the Indiana University-Purdue University Indianapolis and the NSF CHE-1350541 is greatly appreciated for this study. The National Natural Science Foundation of China (No. 21332005, China) and the Robert A. Welch Foundation (D-1361, USA) are also acknowledged. Publisher Copyright: {\textcopyright} 2016 The Royal Society of Chemistry.",

year = "2016",

doi = "10.1039/c6sc01087c",

language = "English",

volume = "7",

pages = "5260--5264",

journal = "Chemical Science",

issn = "2041-6520",

number = "8",

}

TY - JOUR

T1 - Copper-promoted site-selective carbonylation of sp(3) and sp(2) C-H bonds with nitromethane

AU - Wu, Xuesong

AU - Miao, Jinmin

AU - Li, Yanrong

AU - Li, Guigen

AU - Ge, Haibo

N1 - Funding Information: Financial support from the Indiana University-Purdue University Indianapolis and the NSF CHE-1350541 is greatly appreciated for this study. The National Natural Science Foundation of China (No. 21332005, China) and the Robert A. Welch Foundation (D-1361, USA) are also acknowledged. Publisher Copyright: © 2016 The Royal Society of Chemistry.

PY - 2016

Y1 - 2016

N2 - Copper-promoted direct carbonylation of unactivated sp(3)C-H and aromatic sp(2)C-H bonds of amides was developed using nitromethane as a novel carbonyl source. The sp(3)C-H functionalization showed high site-selectivity by favoring the C-H bonds of alpha-methyl groups. The sp(2)C-H carbonylation featured high regioselectivity and good functional group compatibility. Kinetic isotope effect studies indicated that the sp(3)C-H bond breaking step is reversible, whereas the sp(2)C-H bond cleavage is an irreversible but not the rate-determining step. Control experiments showed that a nitromethyl intermediate should be involved in the present reaction.

AB - Copper-promoted direct carbonylation of unactivated sp(3)C-H and aromatic sp(2)C-H bonds of amides was developed using nitromethane as a novel carbonyl source. The sp(3)C-H functionalization showed high site-selectivity by favoring the C-H bonds of alpha-methyl groups. The sp(2)C-H carbonylation featured high regioselectivity and good functional group compatibility. Kinetic isotope effect studies indicated that the sp(3)C-H bond breaking step is reversible, whereas the sp(2)C-H bond cleavage is an irreversible but not the rate-determining step. Control experiments showed that a nitromethyl intermediate should be involved in the present reaction.

UR - http://www.scopus.com/inward/record.url?scp=84979547557&partnerID=8YFLogxK

U2 - 10.1039/c6sc01087c

DO - 10.1039/c6sc01087c

M3 - Article

SN - 2041-6520

VL - 7

SP - 5260

EP - 5264

JO - Chemical Science

JF - Chemical Science

IS - 8

ER -

Copper-promoted site-selective carbonylation of sp(3) and sp(2) C-H bonds with nitromethane

Abstract

Access to Document

Other files and links

Fingerprint

Cite this