Intramolecular C(sp3)-H Bond Oxygenation by Transition-Metal Acylnitrenoids

被引：27

作者：

Tan, Yuqi ^{[1
]}

Chen, Shuming ^{[2
]}

Zhou, Zijun ^{[1
]}

Hong, Yubiao ^{[1
]}

Ivlev, Sergei ^{[1
]}

Houk, K. N. ^{[2
]}

Meggers, Eric ^{[1
]}

机构：

[1] Philipps Univ Marburg, Fachbereich Chem, Hans Meerwein Str 4, D-35043 Marburg, Germany

[2] Univ Calif Los Angeles, Dept Chem & Biochem, Los Angeles, CA 90095 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2020年 / 59卷 / 48期

基金：

美国国家科学基金会;

关键词：

C-H functionalization; enantioselectivity; nitrenoids; oxygenation; ruthenium; NITRENE TRANSFER-REACTIONS; NONHEME IRON CATALYSTS; C-H AMINATION; FUNCTIONALIZATION; OXIDATION; CHALLENGES; INSERTION; CARBENE; COMPLEX;

D O I：

10.1002/anie.202009335

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

This study demonstrates for the first time that easily accessible transition-metal acylnitrenoids can be used for controlled direct C(sp(3))-H oxygenations. Specifically, a ruthenium catalyst activates N-benzoyloxycarbamates as nitrene precursors towards regioselective intramolecular C-H oxygenations to provide cyclic carbonates, hydroxylated carbamates, or 1,2-diols. The method can be applied to the chemoselective C-H oxygenation of benzylic, allylic, and propargylic C(sp(3))-H bonds. The reaction can be performed in an enantioselective fashion and switched in a catalyst-controlled fashion between C-H oxygenation and C-H amination. This work provides a new reaction mode for the regiocontrolled and stereocontrolled conversion of C(sp(3))-H into C(sp(3))-O bonds.

引用

页码：21706 / 21710

页数：5

共 57 条

[1] Recent applications of C-H functionalization in complex natural product synthesis [J].

Abrams, Dylan J. ;

Provencher, Philip A. ;

Sorensen, Erik J. .

CHEMICAL SOCIETY REVIEWS, 2018, 47 (23) :8925-8967

[2]

Bizet V., 2014, ANGEW CHEM, V126, P5745

[3] Light-Induced Ruthenium-Catalyzed Nitrene Transfer Reactions: A Photochemical Approach towards N-Acyl Sulfimides and Sulfoximines [J].

Bizet, Vincent ;

Buglioni, Laura ;

Bolm, Carsten .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (22) :5639-5642

[4] The medicinal chemist's toolbox for late stage functionalization of drug-like molecules [J].

Cernak, Tim ;

Dykstra, Kevin D. ;

Tyagarajan, Sriram ;

Vachal, Petr ;

Krska, Shane W. .

CHEMICAL SOCIETY REVIEWS, 2016, 45 (03) :546-576

[5]

Chu J. C. K., 2018, ANGEW CHEM, V130, P64

[6] Complementary Strategies for Directed C(sp3)-H Functionalization: A Comparison of Transition-Metal-Catalyzed Activation, Hydrogen Atom Transfer, and Carbene/Nitrene Transfer [J].

Chu, John C. K. ;

Rovis, Tomislav .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2018, 57 (01) :62-101

[7] Transition metal-catalyzed iodine(III)-mediated nitrene transfer reactions: efficient tools for challenging syntheses [J].

Darses, B. ;

Rodrigues, R. ;

Neuville, L. ;

Mazurais, M. ;

Dauban, P. .

CHEMICAL COMMUNICATIONS, 2017, 53 (03) :493-508

[8] Catalytic C-H functionalization by metal carbenoid and nitrenoid insertion [J].

Davies, Huw M. L. ;

Manning, James R. .

NATURE, 2008, 451 (7177) :417-424

[9] Collective Approach to Advancing C-H Functionalization [J].

Davies, Huw M. L. ;

Morton, Daniel .

ACS CENTRAL SCIENCE, 2017, 3 (09) :936-943

[10] Nitrene Chemistry in Organic Synthesis: Still in Its Infancy? [J].

Dequirez, Geoffroy ;

Pons, Valerie ;

Dauban, Philippe .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2012, 51 (30) :7384-7395

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