Citation: Qi Zhou, Cefei Zhang, Hui-Lin Luo, Chuan-Xi Nie, Changwei Hu, Jian-Heng Ye, Zhishan Su, Li-Li Liao, Da-Gang Yu. Carbon–metal bond homolysis-recombination enabling enantioconvergent carboxylation with CO₂: A theoretical study[J]. Chinese Chemical Letters, ;2026, 37(5): 111429. doi: 10.1016/j.cclet.2025.111429 shu

Carbon–metal bond homolysis-recombination enabling enantioconvergent carboxylation with CO₂: A theoretical study

Qi Zhou ^a ,
Cefei Zhang ^a ,
Hui-Lin Luo ^a ,
Chuan-Xi Nie ^a ,
Changwei Hu ^a ,
Jian-Heng Ye ^a ,
Zhishan Su ^{a, *,} ,
Li-Li Liao ^{b, *,} ,
Da-Gang Yu ^{a, c, *,}

a.
Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, China
b.
West China School of Public Health and West China Fourth Hospital, Sichuan University, Chengdu 610041, China
c.
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China

suzhishan@scu.edu.cn

liaolili94@scu.edu.cn

dgyu@scu.edu.cn

Received Date: 23 April 2025
Revised Date: 22 May 2025
Accepted Date: 8 June 2025
Available Online: 9 June 2025

Figures(9)

The generation of transient radical species via carbon–metal bond homolysis is extremely useful, which can be harnessed to promote useful and selective radical-type transformations by the combination of transition metal catalysis. We herein establish a carbon–metal bond homolysis/recombination model for the formation of enantiomerically enriched carbon-metal species, which accounts for the Ni-catalyzed enantioconvergent carboxylation of racemic benzyl ammonium salts with CO₂. Theoretical studies suggest a distinct pathway involving a stereoinvertive nucleophilic substitution-type oxidative addition of racemic benzyl ammonium salts to Ni(0), forming a racemic benzyl Ni(Ⅱ) intermediate. Subsequent C–Ni bond homolysis of one enantiomer enables the formation of a transient radical, followed by a dynamic rotation along C–C^· bond and radical recombination forming another more thermodynamically favored enantiomer. Geometry analysis suggests less H–H repulsion between the benzyl group and chiral ligand in the more stable isomer. After the reduction and stereoretentive inner-sphere nucleophilic attack on CO₂ process, the desired enantiomerically enriched carboxylic acid product is generated. ETS-NOCV analysis reveals a significant back-donation interaction between the d_x2-y2 orbital of Ni atom and the unoccupied π* orbital of CO₂ in inner-sphere transition state, thus effectively stabilizing the Ni–CO₂ complex and facilitating subsequent C–C bond formation. The theoretical calculations provide critical insights into the systematic development of transition metal-catalyzed asymmetric carboxylation, highlighting significant potential for broad applications in synthetic organic chemistry.
- Enantioconvergent carboxylation,
- Carbon–metal bond homolysis-recombination,
- Transition metal catalysis,
- DFT calculation,
- Theoretical study
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沈阳化工大学材料科学与工程学院沈阳 110142

Carbon–metal bond homolysis-recombination enabling enantioconvergent carboxylation with CO2: A theoretical study

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Carbon–metal bond homolysis-recombination enabling enantioconvergent carboxylation with CO₂: A theoretical study