Cobalt-Catalyzed Oxidase C-H/N-H Alkyne Annulation: Mechanistic Insights and Access to Anticancer Agents

Ruhuai Mei; Hui Wang; Svenja Warratz; Stuart Alan Macgregor; Lutz Ackermann

doi:10.1002/chem.201601101

Cobalt-Catalyzed Oxidase C-H/N-H Alkyne Annulation: Mechanistic Insights and Access to Anticancer Agents

Ruhuai Mei
, Hui Wang
, Svenja Warratz
, Stuart Alan Macgregor^*
, Lutz Ackermann

^*Corresponding author for this work

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

129 Citations (Scopus)

Abstract

Cp*-free cobalt-catalyzed alkyne annulations by C-H/N-H functionalizations were accomplished with molecular O₂ as the sole oxidant. The user-friendly oxidase strategy proved viable with various internal and terminal alkynes through kinetically relevant C-H cobaltation, providing among others step-economical access to the anticancer topoisomerase-I inhibitor 21,22-dimethoxyrosettacin. DFT calculations suggest that electronic effects control the regioselectivity of the alkyne insertion step.

Original language	English
Pages (from-to)	6759–6763
Number of pages	5
Journal	Chemistry - A European Journal
Volume	22
Issue number	20
Early online date	8 Apr 2016
DOIs	https://doi.org/10.1002/chem.201601101
Publication status	Published - 10 May 2016

Keywords

Annulation
C-H activation
Cobalt
Density functional calculations
Isoquinolones
Oxidase

ASJC Scopus subject areas

General Chemistry

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10.1002/chem.201601101

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title = "Cobalt-Catalyzed Oxidase C-H/N-H Alkyne Annulation: Mechanistic Insights and Access to Anticancer Agents",

abstract = "Cp*-free cobalt-catalyzed alkyne annulations by C-H/N-H functionalizations were accomplished with molecular O2 as the sole oxidant. The user-friendly oxidase strategy proved viable with various internal and terminal alkynes through kinetically relevant C-H cobaltation, providing among others step-economical access to the anticancer topoisomerase-I inhibitor 21,22-dimethoxyrosettacin. DFT calculations suggest that electronic effects control the regioselectivity of the alkyne insertion step.",

keywords = "Annulation, C-H activation, Cobalt, Density functional calculations, Isoquinolones, Oxidase",

author = "Ruhuai Mei and Hui Wang and Svenja Warratz and Macgregor, \{Stuart Alan\} and Lutz Ackermann",

year = "2016",

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T2 - Mechanistic Insights and Access to Anticancer Agents

AU - Mei, Ruhuai

AU - Wang, Hui

AU - Warratz, Svenja

AU - Macgregor, Stuart Alan

AU - Ackermann, Lutz

PY - 2016/5/10

Y1 - 2016/5/10

N2 - Cp*-free cobalt-catalyzed alkyne annulations by C-H/N-H functionalizations were accomplished with molecular O2 as the sole oxidant. The user-friendly oxidase strategy proved viable with various internal and terminal alkynes through kinetically relevant C-H cobaltation, providing among others step-economical access to the anticancer topoisomerase-I inhibitor 21,22-dimethoxyrosettacin. DFT calculations suggest that electronic effects control the regioselectivity of the alkyne insertion step.

AB - Cp*-free cobalt-catalyzed alkyne annulations by C-H/N-H functionalizations were accomplished with molecular O2 as the sole oxidant. The user-friendly oxidase strategy proved viable with various internal and terminal alkynes through kinetically relevant C-H cobaltation, providing among others step-economical access to the anticancer topoisomerase-I inhibitor 21,22-dimethoxyrosettacin. DFT calculations suggest that electronic effects control the regioselectivity of the alkyne insertion step.

KW - Annulation

KW - C-H activation

KW - Cobalt

KW - Density functional calculations

KW - Isoquinolones

KW - Oxidase

UR - https://www.scopus.com/pages/publications/84979486449

U2 - 10.1002/chem.201601101

DO - 10.1002/chem.201601101

M3 - Article

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JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 20

ER -

Cobalt-Catalyzed Oxidase C-H/N-H Alkyne Annulation: Mechanistic Insights and Access to Anticancer Agents

Abstract

Keywords

ASJC Scopus subject areas

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