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

被引:560
作者
Chu, John C. K. [2 ]
Rovis, Tomislav [1 ,2 ]
机构
[1] Columbia Univ, Dept Chem, 3000 Broadway, New York, NY 10027 USA
[2] Colorado State Univ, Dept Chem, Ft Collins, CO 80523 USA
关键词
carbenes; C-H functionalization; hydrogen atom transfer; nitrenes; transition metals; C-H BONDS; RADICAL TRANSLOCATION REACTIONS; LATE-STAGE FUNCTIONALIZATION; ALPHA-AMINO-ACIDS; UNACTIVATED C(SP(3))-H; INTERMOLECULAR AMINATION; INSERTION REACTIONS; ALIPHATIC-AMINES; INTRAMOLECULAR FUNCTIONALIZATION; ENANTIOSELECTIVE SYNTHESIS;
D O I
10.1002/anie.201703743
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The functionalization of C(sp(3))-H bonds streamlines chemical synthesis by allowing the use of simple molecules and providing novel synthetic disconnections. Intensive recent efforts in the development of new reactions based on C-H functionalization have led to its wider adoption across a range of research areas. This Review discusses the strengths and weaknesses of three main approaches: transition-metal-catalyzed C-H activation, 1,n-hydrogen atom transfer, and transition-metal-catalyzed carbene/nitrene transfer, for the directed functionalization of unactivated C(sp(3))-H bonds. For each strategy, the scope, the reactivity of different C-H bonds, the position of the reacting C-H bonds relative to the directing group, and stereochemical outcomes are illustrated with examples in the literature. The aim of this Review is to provide guidance for the use of C-H functionalization reactions and inspire future research in this area.
引用
收藏
页码:62 / 101
页数:40
相关论文
共 275 条
[1]   Nickel-Catalyzed Reaction of C-H Bonds in Amides with I2: ortho-Iodination via the Cleavage of C(sp2)-H Bonds and Oxidative Cyclization to β-Lactams via the Cleavage of C(sp3)-H Bonds [J].
Aihara, Yoshinori ;
Chatani, Naoto .
ACS CATALYSIS, 2016, 6 (07) :4323-4329
[2]   Nickel-Catalyzed Direct Arylation of C(sp3)-H Bonds in Aliphatic Amides via Bidentate-Chelation Assistance [J].
Aihara, Yoshinori ;
Chatani, Naoto .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2014, 136 (03) :898-901
[3]   Enantioselective synthesis of 2-methyl indolines by palladium catalysed asymmetric C(sp3)-H activation/cyclisation [J].
Anas, Saithalavi ;
Cordi, Alex ;
Kagan, Henri B. .
CHEMICAL COMMUNICATIONS, 2011, 47 (41) :11483-11485
[4]   Palladium-Catalyzed Direct Ethynylation of C(sp3)-H Bonds in Aliphatic Carboxylic Acid Derivatives [J].
Ano, Yusuke ;
Tobisu, Mamoru ;
Chatani, Naoto .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (33) :12984-12986
[5]  
[Anonymous], 2012, ANGEW CHEM, DOI DOI 10.1002/ANIE.201201666
[6]  
[Anonymous], 2011, ANGEW CHEM
[7]  
[Anonymous], 2012, ANGEW CHEM, V124, P2281
[8]  
[Anonymous], 2016, ANGEW CHEM, V128, P9230
[9]   CYCLOPALLADATED 2-TERT-BUTYL-4,4-DIMETHYL-2-OXAZOLINE - ITS PREPARATION, AND USE IN THE FUNCTIONALIZATION OF A NONACTIVATED CARBON HYDROGEN-BOND [J].
BALAVOINE, G ;
CLINET, JC .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1990, 390 (03) :C84-C88
[10]  
Baldwin J. E., 1985, TETRAHEDRON, V280, pc51