Chapter 1
Theoretical View of Rh-Catalyzed C–H
Functionalization
Yu Lan
1.1 A Brief History of Rh-Catalyzed C–H Functionalization
1.1.1 General View of Organometallic Chemistry
The synthetic organic chemistry usually focuses on “carbon” to spread related
research, which could afford various strategies for the building of molecular framework, functional group transformations, and controlling stereochemistry in more
sophisticated molecules [1–13]. Therefore, selective formation of the new covalent
bond between the carbon atom and some other atoms, involving nitrogen, oxygen,
sulfur, halogen, boron, and phosphorus, becomes one of the most important aims for
synthetic organic chemistry [14, 15]. The coupling reactions provide practical and
efficient methods for the formation of new carbon–carbon and carbon–heteroatom
bonds [16–25]. Generally, cross-coupling reactions build covalent bonds between
nucleophiles and electrophiles [26–33]. Reductive coupling combines two electrophiles by gaining electrons from reductive agents [34–40]. When oxidations are
involved, two nucleophiles would conduct oxidative coupling to lose electrons and
form carbon–carbon and carbon–heteroatom bonds [41–47] (Scheme 1.1).
In organic chemistry, the nucleophile is an electron-rich molecule that contains
a lone pair of electrons or a polarized bond, the heterolysis of which also could
yield a lone pair of elections [48–50] (Scheme 1.2). According to this concept,
organometallic compounds, alcohols, halides, amines, and phosphines with a lone
pair of electrons are nucleophiles [51–55]. Some nonpolar π bonds including olefins
and acetylenes, which could donate the π bonding electrons, are often considered to
be nucleophiles [56–58]. Moreover, the C–H bonds of hydrocarbons can be considered to be nucleophiles because the electronegativity of carbon is higher than that of
hydrogen, which could deliver a proton to form a formal carbon anion [59–65].
Correspondingly, the electrophile is an electron-deficient molecule that contains
unoccupied orbitals or low energy antibonding molecular orbital, which could accept
© 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_1
1
Theoretical View of Rh-Catalyzed C–H
Functionalization
Yu Lan
1.1 A Brief History of Rh-Catalyzed C–H Functionalization
1.1.1 General View of Organometallic Chemistry
The synthetic organic chemistry usually focuses on “carbon” to spread related
research, which could afford various strategies for the building of molecular framework, functional group transformations, and controlling stereochemistry in more
sophisticated molecules [1–13]. Therefore, selective formation of the new covalent
bond between the carbon atom and some other atoms, involving nitrogen, oxygen,
sulfur, halogen, boron, and phosphorus, becomes one of the most important aims for
synthetic organic chemistry [14, 15]. The coupling reactions provide practical and
efficient methods for the formation of new carbon–carbon and carbon–heteroatom
bonds [16–25]. Generally, cross-coupling reactions build covalent bonds between
nucleophiles and electrophiles [26–33]. Reductive coupling combines two electrophiles by gaining electrons from reductive agents [34–40]. When oxidations are
involved, two nucleophiles would conduct oxidative coupling to lose electrons and
form carbon–carbon and carbon–heteroatom bonds [41–47] (Scheme 1.1).
In organic chemistry, the nucleophile is an electron-rich molecule that contains
a lone pair of electrons or a polarized bond, the heterolysis of which also could
yield a lone pair of elections [48–50] (Scheme 1.2). According to this concept,
organometallic compounds, alcohols, halides, amines, and phosphines with a lone
pair of electrons are nucleophiles [51–55]. Some nonpolar π bonds including olefins
and acetylenes, which could donate the π bonding electrons, are often considered to
be nucleophiles [56–58]. Moreover, the C–H bonds of hydrocarbons can be considered to be nucleophiles because the electronegativity of carbon is higher than that of
hydrogen, which could deliver a proton to form a formal carbon anion [59–65].
Correspondingly, the electrophile is an electron-deficient molecule that contains
unoccupied orbitals or low energy antibonding molecular orbital, which could accept
© 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_1
1