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© Springer-Verlag GmbH Germany, part of Springer Nature 2019
A. Lei (ed.), Transition Metal Catalyzed Oxidative Cross-Coupling Reactions,
Lecture Notes in Chemistry 102, https://doi.org/10.1007/978-3-662-58104-9_5
Chapter 5
Fourth-Generation Oxidative
Cross- Coupling Reactions
Wenying Ai, Bin Li, and Qiang Liu
In the last chapter, we introduced the direct construction of a C-C or C-X (X = heteroatom) bond from two different C-H/C-H or C-H/X-H bonds via oxidative crosscoupling reactions. However, an external oxidant needs to be present in the system
to remove excess protons and electrons generated during the formation of the C-C
or C-X bond. To obviate the need for sacrificial oxidants and realize a more sustainable coupling reaction mode, a fourth-generation oxidative cross-coupling strategy
has been developed in recent years, which is oxidant-free and yields hydrogen (H 2 )
gas as the only by-product [1] (Scheme 5.1). This transformation is an ideal green
coupling reaction process; however, the loss of H 2 in this reaction is usually thermodynamically unfavorable. Therefore, input of external energy, including thermal
energy, light energy, or electrical energy, is required to provide a thermodynamic
driving force. In this chapter, we summarize the impressive progress of fourthgeneration oxidative coupling reactions, which is divided into three parts: (1) thermal energy-driven cross-coupling reactions with H 2 evolution, (2)
visible-light-mediated cross-coupling reactions with H 2 evolution, and (3) electrochemical dehydrogenative reactions with H 2 evolution.
W. Ai
Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University,
Beijing, China
B. Li (*)
School of Chemical & Environmental Engineering, Wuyi University,
Jiangmen, Guangdong, People’s Republic of China
Q. Liu (*)
School of Chemical & Environmental Engineering, Wuyi University,
Jiangmen, Guangdong, People’s Republic of China
Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University,
Beijing, China
e-mail: qiang_liu@mail.tsinghua.edu.cn
© Springer-Verlag GmbH Germany, part of Springer Nature 2019
A. Lei (ed.), Transition Metal Catalyzed Oxidative Cross-Coupling Reactions,
Lecture Notes in Chemistry 102, https://doi.org/10.1007/978-3-662-58104-9_5
Chapter 5
Fourth-Generation Oxidative
Cross- Coupling Reactions
Wenying Ai, Bin Li, and Qiang Liu
In the last chapter, we introduced the direct construction of a C-C or C-X (X = heteroatom) bond from two different C-H/C-H or C-H/X-H bonds via oxidative crosscoupling reactions. However, an external oxidant needs to be present in the system
to remove excess protons and electrons generated during the formation of the C-C
or C-X bond. To obviate the need for sacrificial oxidants and realize a more sustainable coupling reaction mode, a fourth-generation oxidative cross-coupling strategy
has been developed in recent years, which is oxidant-free and yields hydrogen (H 2 )
gas as the only by-product [1] (Scheme 5.1). This transformation is an ideal green
coupling reaction process; however, the loss of H 2 in this reaction is usually thermodynamically unfavorable. Therefore, input of external energy, including thermal
energy, light energy, or electrical energy, is required to provide a thermodynamic
driving force. In this chapter, we summarize the impressive progress of fourthgeneration oxidative coupling reactions, which is divided into three parts: (1) thermal energy-driven cross-coupling reactions with H 2 evolution, (2)
visible-light-mediated cross-coupling reactions with H 2 evolution, and (3) electrochemical dehydrogenative reactions with H 2 evolution.
W. Ai
Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University,
Beijing, China
B. Li (*)
School of Chemical & Environmental Engineering, Wuyi University,
Jiangmen, Guangdong, People’s Republic of China
Q. Liu (*)
School of Chemical & Environmental Engineering, Wuyi University,
Jiangmen, Guangdong, People’s Republic of China
Center of Basic Molecular Science (CBMS), Department of Chemistry, Tsinghua University,
Beijing, China
e-mail: qiang_liu@mail.tsinghua.edu.cn