Intermolecular C(sp3)-H Amination of Complex Molecules

被引：82

作者：

Chiappini, Nicholas D. ^{[1
]}

Mack, James B. C. ^{[1
]}

Du Bois, J. ^{[1
]}

机构：

[1] Stanford Univ, Dept Chem, Stanford, CA 94305 USA

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2018年 / 57卷 / 18期

基金：

美国国家科学基金会;

关键词：

amination; C-H oxidation; reaction mechanisms; rhodium; sulfamates; C-H AMINATION; NITRENE TRANSFER-REACTIONS; BOND AMINATION; CATALYST; FUNCTIONALIZATION; AZIRIDINATION; RH-2(ESP)(2); CARBOXYLATE; CHALLENGES; ASSIGNMENT;

D O I：

10.1002/anie.201713225

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A general and operationally convenient method for intermolecular amination of C(sp(3))-H bonds is described. This technology allows for efficient functionalization of complex molecules, including numerous pharmaceutical targets. The combination of pivalonitrile as a solvent, Al2O3 as an additive, and phenyl sulfamate as a nitrogen source affords differential reaction performance and substrate scope. Mechanistic data strongly implicate a pathway for catalyst decomposition that initiates with solvent oxidation, thus providing rationale for the marked influence of pivalonitrile on this reaction process.

引用

页码：4956 / 4959

页数：4

共 45 条

[1]

Bakhoda A., 2017, Angew. Chem. Int. Ed, V129, P6526

[2] Elusive Terminal Copper Arylnitrene Intermediates [J].

Bakhoda, Abolghasem ;

Jiang, Quan ;

Bertke, Jeffery A. ;

Cundari, Thomas R. ;

Warren, Timothy H. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2017, 56 (23) :6426-6430

[3] Tunable differentiation of tertiary C-H bonds in intramolecular transition metal-catalyzed nitrene transfer reactions [J].

Corbin, Joshua R. ;

Schomaker, Jennifer M. .

CHEMICAL COMMUNICATIONS, 2017, 53 (31) :4346-4349

[4] The first dirhodium tetracarboxylate molecule without axial ligation: New insight into the electronic structures of molecules with importance in catalysis and other reactions [J].

Cotton, FA ;

Hillard, EA ;

Murillo, CA .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (20) :5658-5660

[5] STRUCTURAL STUDIES OF 3 TETRAKIS(CARBOXYLATO)DIRHODIUM(II) ADDUCTS IN WHICH CARBOXYLATE GROUPS AND AXIAL LIGANDS ARE VARIED [J].

COTTON, FA ;

FELTHOUSE, TR .

INORGANIC CHEMISTRY, 1980, 19 (02) :323-328

[6] 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

[7] Catalyst-Controlled and Tunable, Chemoselective Silver-Catalyzed Intermolecular Nitrene Transfer: Experimental and Computational Studies [J].

Dolan, Nicholas S. ;

Scamp, Ryan J. ;

Yang, Tzuhsiung ;

Berry, John F. ;

Schomaker, Jennifer M. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2016, 138 (44) :14658-14667

[8] QUANTITATIVE STUDIES OF CHEMICAL-REACTIVITY OF TETRA-MU-BUTYRATO-DIRHODIUM(II) COMPLEXES [J].

DRAGO, RS ;

TANNER, SP ;

RICHMAN, RM ;

LONG, JR .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1979, 101 (11) :2897-2903

[9] Chemoselective, Enzymatic C-H Bond Amination Catalyzed by a Cytochrome P450 Containing an Ir(Me)-PIX Cofactor [J].

Dydio, Pawel ;

Key, Hanna M. ;

Hayashi, Hiroki ;

Clark, Douglas S. ;

Hartwig, John F. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2017, 139 (05) :1750-1753

[10] Catalytic intermolecular amination of C-H bonds: Method development and mechanistic insights [J].

Fiori, Kristin Williams ;

Du Bois, J. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (03) :562-568

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