Citation: Deng Pan, Chuan He, Genping Huang. Mechanism and origins of enantioselectivity of iridium-catalyzed atroposelective intermolecular C(sp²)-H silylation: A ligand-enabled axial chirality transfer strategy[J]. Chinese Chemical Letters, ;2026, 37(4): 111217. doi: 10.1016/j.cclet.2025.111217 shu

Mechanism and origins of enantioselectivity of iridium-catalyzed atroposelective intermolecular C(sp²)-H silylation: A ligand-enabled axial chirality transfer strategy

Deng Pan ^a ,
Chuan He ^{b, *,} ,
Genping Huang ^{a, *,}

a.
Department of Chemistry, School of Science, Tianjin University, Tianjin 300072, China
b.
Shenzhen Grubbs Institute and Department of Chemistry, Shenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen 518055, China

hec@sustech.edu.cn

gphuang@tju.edu.cn

Received Date: 14 January 2025
Revised Date: 6 April 2025
Accepted Date: 15 April 2025
Available Online: 17 April 2025

Figures(4)

Density functional theory calculations were performed to investigate the iridium-catalyzed atroposelective intermolecular C-H silylation of 2-arylisoquinolines. The Ir(Ⅲ) hydride species was identified as the active catalyst species of the reaction. The computations show that the reaction occurs through the Ir(Ⅲ)/Ir(V) catalytic cycle. The C(sp²)-H oxidative addition represents the rate- and enantioselectivity-determining step. The distortion/interaction and structural analyses reveal that the BINEPINE skeleton of the PSiSi ligand creates an axially chiral pocket for the C-H oxidative addition, providing a ligand-enabled axial chirality transfer strategy responsible for the observed enantioselectivity. The match/mismatch in axial chirality between reacting 2-arylisoquinolines and the BINEPINE skeleton of the PSiSi ligand plays a key role in governing enantioselectivity.
- C-H silylation,
- Iridium,
- DFT calculations,
- Reaction mechanism,
- enantioselectivity
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沈阳化工大学材料科学与工程学院沈阳 110142

Mechanism and origins of enantioselectivity of iridium-catalyzed atroposelective intermolecular C(sp2)-H silylation: A ligand-enabled axial chirality transfer strategy

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通讯作者: 陈斌, bchen63@163.com

Mechanism and origins of enantioselectivity of iridium-catalyzed atroposelective intermolecular C(sp²)-H silylation: A ligand-enabled axial chirality transfer strategy