Contents
1 Theoretical View of Rh-Catalyzed C–H Functionalization . . . . . . . . . .
1
Yu Lan
1.1 A Brief History of Rh-Catalyzed C–H Functionalization . . . . . . . . .
1
1.1.1 General View of Organometallic Chemistry . . . . . . . . . . . . . .
1
1.1.2 A Brief History of Rh-Catalyzed C–H
Functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4
1.2 Using Computational Tool to Study the Mechanism
of Rh-Catalyzed C–H Functionalization . . . . . . . . . . . . . . . . . . . . . . .
9
1.2.1 Mechanism of Rh-Catalyzed C–H Functionalization . . . . . .
9
1.2.2 Mechanistic Study of Rh-Catalyzed C–H
Functionalization by Theoretical Methods . . . . . . . . . . . . . . . 11
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2 Computational Methods in Rh-Catalyzed C–H
Functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Cheng-Xing Cui, Song Liu, Chun-Xiang Li, Ruopeng Bai, and Yu Lan
2.1 DFT Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.1.1 Basis Set . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.1.2 Solvent Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3 Theoretical Study of Rh-Catalyzed C–C Bond Formation
Through C–H Activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Song Liu, Cheng-Xing Cui, Ruopeng Bai, Chun-Xiang Li, and Yu Lan
3.1 Rh-Catalyzed C–H Bond Arylation . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3.1.1 C–H Bond Arylation with Electrophiles . . . . . . . . . . . . . . . . . 28
3.2 Rh-Catalyzed C–H Bond Alkylation . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.2.1 C–H Bond Alkylation by Using Olefins . . . . . . . . . . . . . . . . . 36
3.2.2 C–H Bond Alkylation by Using Alkynes . . . . . . . . . . . . . . . . 43
3.2.3 C–H Bond Alkylation by Using Diazo Compound . . . . . . . . 46
3.3 Rh-Catalyzed C–H Bond Alkenylation . . . . . . . . . . . . . . . . . . . . . . . . 48
3.3.1 C–H Bond Alkenylation by Using Olefins . . . . . . . . . . . . . . . 48
3.3.2 C–H Bond Alkenylation by Using Alkynes . . . . . . . . . . . . . . 51
vii
1 Theoretical View of Rh-Catalyzed C–H Functionalization . . . . . . . . . .
1
Yu Lan
1.1 A Brief History of Rh-Catalyzed C–H Functionalization . . . . . . . . .
1
1.1.1 General View of Organometallic Chemistry . . . . . . . . . . . . . .
1
1.1.2 A Brief History of Rh-Catalyzed C–H
Functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4
1.2 Using Computational Tool to Study the Mechanism
of Rh-Catalyzed C–H Functionalization . . . . . . . . . . . . . . . . . . . . . . .
9
1.2.1 Mechanism of Rh-Catalyzed C–H Functionalization . . . . . .
9
1.2.2 Mechanistic Study of Rh-Catalyzed C–H
Functionalization by Theoretical Methods . . . . . . . . . . . . . . . 11
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2 Computational Methods in Rh-Catalyzed C–H
Functionalization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Cheng-Xing Cui, Song Liu, Chun-Xiang Li, Ruopeng Bai, and Yu Lan
2.1 DFT Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
2.1.1 Basis Set . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
2.1.2 Solvent Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
3 Theoretical Study of Rh-Catalyzed C–C Bond Formation
Through C–H Activation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
Song Liu, Cheng-Xing Cui, Ruopeng Bai, Chun-Xiang Li, and Yu Lan
3.1 Rh-Catalyzed C–H Bond Arylation . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
3.1.1 C–H Bond Arylation with Electrophiles . . . . . . . . . . . . . . . . . 28
3.2 Rh-Catalyzed C–H Bond Alkylation . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.2.1 C–H Bond Alkylation by Using Olefins . . . . . . . . . . . . . . . . . 36
3.2.2 C–H Bond Alkylation by Using Alkynes . . . . . . . . . . . . . . . . 43
3.2.3 C–H Bond Alkylation by Using Diazo Compound . . . . . . . . 46
3.3 Rh-Catalyzed C–H Bond Alkenylation . . . . . . . . . . . . . . . . . . . . . . . . 48
3.3.1 C–H Bond Alkenylation by Using Olefins . . . . . . . . . . . . . . . 48
3.3.2 C–H Bond Alkenylation by Using Alkynes . . . . . . . . . . . . . . 51
vii