Top Organomet Chem (2016) 56: 115–132
DOI: 10.1007/3418_2015_136
# Springer International Publishing Switzerland 2015
Published online: 23 July 2015
Silver-Mediated Direct sp
3 C–H Bond
Functionalization
Taigang Zhou and Zhang-Jie Shi
Abstract Direct sp
3 C–H bond functionalization is an efficient, straightforward,
and powerful method to construct new C–X (X¼C, N, F, S) bonds from
nonfunctionalized aliphatic motif of organic molecules, which has been used in
late-stage modification of complex molecules. In this chapter, the recent developments of silver-mediated direct sp
3 C–H functionalizations are reviewed, categorized by C–C bond formation (C–H insertion), C–N bond formation (intramolecular
and intermolecular amination/amidation), C–F bond formation, and C–S bond
formation.
Keywords C–X (X¼C, N, F, S) formation • Silver • sp
3 C–H functionalization
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
2 Silver-Mediated Direct sp
3 C–H Transformations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
2.1 Direct C–C Bond Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
2.2 Direct C–N Bond Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
2.3 Direct C–F Bond Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
2.4 Direct C–SCF 3 Bond Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
3 Conclusions and Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
T. Zhou
College of Chemistry, Peking University, Beijing 100871, China
Z.-J. Shi (*)
College of Chemistry, Peking University, Beijing 100871, China
State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, Shanghai
200032, China
e-mail: zshi@pku.edu.cn
DOI: 10.1007/3418_2015_136
# Springer International Publishing Switzerland 2015
Published online: 23 July 2015
Silver-Mediated Direct sp
3 C–H Bond
Functionalization
Taigang Zhou and Zhang-Jie Shi
Abstract Direct sp
3 C–H bond functionalization is an efficient, straightforward,
and powerful method to construct new C–X (X¼C, N, F, S) bonds from
nonfunctionalized aliphatic motif of organic molecules, which has been used in
late-stage modification of complex molecules. In this chapter, the recent developments of silver-mediated direct sp
3 C–H functionalizations are reviewed, categorized by C–C bond formation (C–H insertion), C–N bond formation (intramolecular
and intermolecular amination/amidation), C–F bond formation, and C–S bond
formation.
Keywords C–X (X¼C, N, F, S) formation • Silver • sp
3 C–H functionalization
Contents
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
2 Silver-Mediated Direct sp
3 C–H Transformations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
2.1 Direct C–C Bond Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
2.2 Direct C–N Bond Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
2.3 Direct C–F Bond Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
2.4 Direct C–SCF 3 Bond Formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
3 Conclusions and Perspective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
T. Zhou
College of Chemistry, Peking University, Beijing 100871, China
Z.-J. Shi (*)
College of Chemistry, Peking University, Beijing 100871, China
State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, Shanghai
200032, China
e-mail: zshi@pku.edu.cn