Chapter 4
Theoretical View of Rh-Catalyzed C–H
Functionalization for the Construction of
C–X Bonds (X = O, N, B, Si, or Halide)
Chun-Xiang Li, Ruopeng Bai, Song Liu, Cheng-Xing Cui, and Yu Lan
The C–heteroatom bonds can be constructed by selecting particular substrates that
contain heteroatoms through Rh-catalyzed C–H bond functionalization. Despite the
dominance of C–C bond formation reactions, Rh-catalyzed C–X (X = N, O, halide,
B, Si) bond formation reactions through C–H bond activations have also been well
developed and studied in detail recently [1–14]. Given the synthetic utility of C–
heteroatom bond formation and functionalization, it is not surprising that much effort
has recently been put forth towards the development of new transformations that focus
on Rh-catalyzed direct functionalization of C–H bonds to C–X bonds. Despite the
pertinent reviews about these transformations that have been emerged, these reviews
tend to focus on catalytic reactions, and mechanistic data are often speculative. In this
part, we present an overview of the theoretical studies of Rh-catalyzed C–H bond
activation and C–X (X = N, O, halide, B, Si) bond formation. These theoretical
studies provide valuable insight into the mechanism and the origin of the regio- and
stereoselectivity for these Rh-catalyzed C–H bond activation reactions.
4.1 C–O Bond Formation
The Rh-mediated C–H activation often provides a nucleophilic aryl group, which can
react with an electrophilic oxygen for the construction of C–O bond. In 2018, Yang
and co-workers [15] reported a Rh(III)-catalyzed C(sp
2 )–H benzoxylation reaction,
where a hypervalent iodine reagent is used to offer electrophilic oxygen. The kinetic
isotope effect experiment (k H /k D = 3.3) indicates that the C–H bond cleavage is
likely involved in the turnover-limiting step. In addition, the cyclometalated Rh(III)
complex 4-1 was separated and successfully catalyzed this benzoxylation reaction,
which suggests that complex 4-1 is the plausible key intermediate that participated
in the catalytic cycle (Scheme 4.1).
© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2021
Y. Lan et al., Computational Advances of Rh-Catalyzed C–H Functionalization,
SpringerBriefs in Molecular Science,
https://doi.org/10.1007/978-981-16-0432-4_4
97
Theoretical View of Rh-Catalyzed C–H
Functionalization for the Construction of
C–X Bonds (X = O, N, B, Si, or Halide)
Chun-Xiang Li, Ruopeng Bai, Song Liu, Cheng-Xing Cui, and Yu Lan
The C–heteroatom bonds can be constructed by selecting particular substrates that
contain heteroatoms through Rh-catalyzed C–H bond functionalization. Despite the
dominance of C–C bond formation reactions, Rh-catalyzed C–X (X = N, O, halide,
B, Si) bond formation reactions through C–H bond activations have also been well
developed and studied in detail recently [1–14]. Given the synthetic utility of C–
heteroatom bond formation and functionalization, it is not surprising that much effort
has recently been put forth towards the development of new transformations that focus
on Rh-catalyzed direct functionalization of C–H bonds to C–X bonds. Despite the
pertinent reviews about these transformations that have been emerged, these reviews
tend to focus on catalytic reactions, and mechanistic data are often speculative. In this
part, we present an overview of the theoretical studies of Rh-catalyzed C–H bond
activation and C–X (X = N, O, halide, B, Si) bond formation. These theoretical
studies provide valuable insight into the mechanism and the origin of the regio- and
stereoselectivity for these Rh-catalyzed C–H bond activation reactions.
4.1 C–O Bond Formation
The Rh-mediated C–H activation often provides a nucleophilic aryl group, which can
react with an electrophilic oxygen for the construction of C–O bond. In 2018, Yang
and co-workers [15] reported a Rh(III)-catalyzed C(sp
2 )–H benzoxylation reaction,
where a hypervalent iodine reagent is used to offer electrophilic oxygen. The kinetic
isotope effect experiment (k H /k D = 3.3) indicates that the C–H bond cleavage is
likely involved in the turnover-limiting step. In addition, the cyclometalated Rh(III)
complex 4-1 was separated and successfully catalyzed this benzoxylation reaction,
which suggests that complex 4-1 is the plausible key intermediate that participated
in the catalytic cycle (Scheme 4.1).
© The Author(s), under exclusive license to Springer Nature Singapore Pte Ltd. 2021
Y. Lan et al., Computational Advances of Rh-Catalyzed C–H Functionalization,
SpringerBriefs in Molecular Science,
https://doi.org/10.1007/978-981-16-0432-4_4
97