Chapter 3
Theoretical Study of Rh-Catalyzed C–C
Bond Formation Through C–H
Activation
Song Liu, Cheng-Xing Cui, Ruopeng Bai, Chun-Xiang Li, and Yu Lan
Construction of C–C bonds is a considerable area in both academic and industrial
fields [1, 2]. The ubiquity and low cost of hydrocarbons make C–H bond functionalization to be an attractive alternative to classical transition metal-catalyzed
cross-coupling reactions with functionalized organic compounds [2–7]. In the last
few decades, numerous synthetic methods have been devoted to form C–C bonds and
lengthen carbon chains through C–H bond functionalization. It’s worth noting that
the introduction of transition metal makes C–H bond functionalization to be a facile
process. Among these transition metals, Rh [8–16] used as catalysts stands out for
their functional group tolerance and wide range of synthetic utility in the C–C bond
formation reactions with C–H bonds. In a series of pioneering works, a variety of
Rh-catalyzed C–C coupling reactions with C–H bonds have been reported [17, 18].
Because of the complexity of the C–H bond activation reaction itself and its mechanism, the computational study processes have witnessed tremendous development to
aid in the design of Rh-catalyzed C–C coupling reactions with C–H bonds [19, 20].
In particular, the theoretical studies of Rh-catalyzed C–H bond arylation, alkylation,
vinylation, alkynylation, carbonylation, and annulation have been of interest, which
would be discussed in detail.
The C–H bonds can be considered nucleophile because the electronegativity of
carbon is higher than that of hydrogen in this moiety. Therefore, the C–H bond can
formally donate both of their bonding electrons to an electrophile to form a new
C–C σ-bond through redox-neutral cross-coupling. Alternatively, C–H bonds also
can couple with a nucleophile in the presence of exogenous oxidants, which results
in oxidative-coupling reactions (Scheme 3.1). In this case, the exogenous oxidant
removes one pair of electrons from C–H bond and another nucleophile to build a
new C–C σ-bond.
© 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_3
27
Theoretical Study of Rh-Catalyzed C–C
Bond Formation Through C–H
Activation
Song Liu, Cheng-Xing Cui, Ruopeng Bai, Chun-Xiang Li, and Yu Lan
Construction of C–C bonds is a considerable area in both academic and industrial
fields [1, 2]. The ubiquity and low cost of hydrocarbons make C–H bond functionalization to be an attractive alternative to classical transition metal-catalyzed
cross-coupling reactions with functionalized organic compounds [2–7]. In the last
few decades, numerous synthetic methods have been devoted to form C–C bonds and
lengthen carbon chains through C–H bond functionalization. It’s worth noting that
the introduction of transition metal makes C–H bond functionalization to be a facile
process. Among these transition metals, Rh [8–16] used as catalysts stands out for
their functional group tolerance and wide range of synthetic utility in the C–C bond
formation reactions with C–H bonds. In a series of pioneering works, a variety of
Rh-catalyzed C–C coupling reactions with C–H bonds have been reported [17, 18].
Because of the complexity of the C–H bond activation reaction itself and its mechanism, the computational study processes have witnessed tremendous development to
aid in the design of Rh-catalyzed C–C coupling reactions with C–H bonds [19, 20].
In particular, the theoretical studies of Rh-catalyzed C–H bond arylation, alkylation,
vinylation, alkynylation, carbonylation, and annulation have been of interest, which
would be discussed in detail.
The C–H bonds can be considered nucleophile because the electronegativity of
carbon is higher than that of hydrogen in this moiety. Therefore, the C–H bond can
formally donate both of their bonding electrons to an electrophile to form a new
C–C σ-bond through redox-neutral cross-coupling. Alternatively, C–H bonds also
can couple with a nucleophile in the presence of exogenous oxidants, which results
in oxidative-coupling reactions (Scheme 3.1). In this case, the exogenous oxidant
removes one pair of electrons from C–H bond and another nucleophile to build a
new C–C σ-bond.
© 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_3
27