Cobalt-Catalyzed Intramolecular Hydroacylation Involving Cyclopropane Cleavage

Junfeng Yang; Yuto Mori; Masahiro Yamanaka; Naohiko Yoshikai

doi:10.1002/chem.202001223

Cobalt-Catalyzed Intramolecular Hydroacylation Involving Cyclopropane Cleavage

Junfeng Yang, Yuto Mori, Masahiro Yamanaka, Naohiko Yoshikai

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

4 Citations (Scopus)

Abstract

A simple cobalt-diphosphine catalyst has been found to efficiently promote intramolecular cyclization of ortho-cyclopropylvinyl- and cyclopropylidenemethyl-substituted benzaldehydes into benzocyclooctadienone and benzocycloheptadienone derivatives, respectively. This ring-opening hydroacylation likely involves aldehyde C−H oxidative addition, olefin insertion, cyclopropane cleavage by β-carbon elimination, and C−C bond-forming reductive elimination, as was supported by mechanistic experiments and DFT calculations.

Original language	English
Pages (from-to)	8302-8307
Number of pages	6
Journal	Chemistry - A European Journal
Volume	26
Issue number	37
DOIs	https://doi.org/10.1002/chem.202001223
Publication status	Published - 2020 Jul 2
Externally published	Yes

Keywords

C−C bond cleavage
C−H activation
cobalt
cyclopropanes
hydroacylation

ASJC Scopus subject areas

Catalysis
Organic Chemistry

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10.1002/chem.202001223

Cite this

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title = "Cobalt-Catalyzed Intramolecular Hydroacylation Involving Cyclopropane Cleavage",

abstract = "A simple cobalt-diphosphine catalyst has been found to efficiently promote intramolecular cyclization of ortho-cyclopropylvinyl- and cyclopropylidenemethyl-substituted benzaldehydes into benzocyclooctadienone and benzocycloheptadienone derivatives, respectively. This ring-opening hydroacylation likely involves aldehyde C−H oxidative addition, olefin insertion, cyclopropane cleavage by β-carbon elimination, and C−C bond-forming reductive elimination, as was supported by mechanistic experiments and DFT calculations.",

keywords = "C−C bond cleavage, C−H activation, cobalt, cyclopropanes, hydroacylation",

author = "Junfeng Yang and Yuto Mori and Masahiro Yamanaka and Naohiko Yoshikai",

note = "Funding Information: This work was supported by the Ministry of Education (Singapore) and Nanyang Technological University (MOE2016‐T2‐2‐043, RG114/18 to N.Y.), JSPS KAKENHI (Grant Number JP17KT0011 to M.Y.), and National Natural Science Foundation of China (21901043 to J.Y.). Publisher Copyright: {\textcopyright} 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

year = "2020",

month = jul,

day = "2",

doi = "10.1002/chem.202001223",

language = "English",

volume = "26",

pages = "8302--8307",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag",

number = "37",

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TY - JOUR

T1 - Cobalt-Catalyzed Intramolecular Hydroacylation Involving Cyclopropane Cleavage

AU - Yang, Junfeng

AU - Mori, Yuto

AU - Yamanaka, Masahiro

AU - Yoshikai, Naohiko

N1 - Funding Information: This work was supported by the Ministry of Education (Singapore) and Nanyang Technological University (MOE2016‐T2‐2‐043, RG114/18 to N.Y.), JSPS KAKENHI (Grant Number JP17KT0011 to M.Y.), and National Natural Science Foundation of China (21901043 to J.Y.). Publisher Copyright: © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2020/7/2

Y1 - 2020/7/2

N2 - A simple cobalt-diphosphine catalyst has been found to efficiently promote intramolecular cyclization of ortho-cyclopropylvinyl- and cyclopropylidenemethyl-substituted benzaldehydes into benzocyclooctadienone and benzocycloheptadienone derivatives, respectively. This ring-opening hydroacylation likely involves aldehyde C−H oxidative addition, olefin insertion, cyclopropane cleavage by β-carbon elimination, and C−C bond-forming reductive elimination, as was supported by mechanistic experiments and DFT calculations.

AB - A simple cobalt-diphosphine catalyst has been found to efficiently promote intramolecular cyclization of ortho-cyclopropylvinyl- and cyclopropylidenemethyl-substituted benzaldehydes into benzocyclooctadienone and benzocycloheptadienone derivatives, respectively. This ring-opening hydroacylation likely involves aldehyde C−H oxidative addition, olefin insertion, cyclopropane cleavage by β-carbon elimination, and C−C bond-forming reductive elimination, as was supported by mechanistic experiments and DFT calculations.

KW - C−C bond cleavage

KW - C−H activation

KW - cobalt

KW - cyclopropanes

KW - hydroacylation

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U2 - 10.1002/chem.202001223

DO - 10.1002/chem.202001223

M3 - Article

C2 - 32291843

AN - SCOPUS:85087405735

SN - 0947-6539

VL - 26

SP - 8302

EP - 8307

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 37

ER -

Cobalt-Catalyzed Intramolecular Hydroacylation Involving Cyclopropane Cleavage

Abstract

Keywords

ASJC Scopus subject areas

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