Visible-light photocatalytic 1,1-difunctionalizing carboxylation of isocyanides with CO2

doi:10.1016/S1872-2067(26)65211-4

Abstract

Abstract:

Difunctionalizing carboxylation of unsaturated compounds with CO₂ has emerged as a powerful strategy for synthesizing functionalized carboxylic acids. While substantial progress has been made, existing approaches have predominantly focused on 1,2-difunctionalizing carboxylation processes. Herein, we report the first 1,1-difunctionalizing carboxylation of isocyanides with CO₂, enabling the efficient construction of diverse N-heteroaromatic carboxylic acids under mild conditions. This visible-light photocatalytic protocol displays broad substrate scope, good functional group tolerance, ready scalability and facile late-stage derivatization. Mechanistic studies and density functional theory calculations reveal that the generated electron-donor-acceptor complex could facilitate the formation of isocyanide- or CO₂-derived radical anions, according to their redox potentials and stability. These radical anion intermediates could undergo following carboxylation to afford diverse N-heteroaromatic carboxylic acids.

Key words: Carbon dioxide, Visible-light photocatalysis, Radical anion, Electron-donor-acceptor complex, 1,1-Difunctionalizing carboxylation

Yuan-Xu Jiang, Zhi-Xin Yan, Long-Fu Wang, Yi-Chi Chen, Wen-Hao Xu, Shu-Rong Zhang, Jun-Ping Yue, Min Pan, Yong-Yuan Gui, Lei Song, Li-Li Liao, Jian-Heng Ye, Da-Gang Yu. Visible-light photocatalytic 1,1-difunctionalizing carboxylation of isocyanides with CO₂[J]. Chinese Journal of Catalysis, 2026, 91: 93-102.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65211-4

https://www.cjcatal.com/EN/Y2026/V91/I12/93

Figures/Tables 8

Fig. 1. Schematic illustration of radical anion-involved carboxylation with CO2.

Table 1 Optimization of the reaction conditions a.

Table 2 Substrate scope of biphenyl isocyanides a.

Table 3 Substrate scope of 2-isocyanoaryl thioethers and selenides a.

Scheme 1. Schematic illustration for synthetic transformations including gram-scale synthesis and late-stage derivatization.

Scheme 2. Mechanistic investigations of the photocatalytic carboxylation reaction.

Scheme 3. Computational studies. All energies are in kcal mol-1 and represent the relative free energies calculated at the B3LYP/6-311+G(d,p)/SMD(DMAc)//B3LYP/6-31+G(d)/SMD(DMAc) level of theory. The bond lengths are reported in angstroms (Å).

Scheme 4. Proposed plausible reaction mechanism for the 1,1-difunctionalizing carboxylation of isocyanides with CO2.

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Visible-light photocatalytic 1,1-difunctionalizing carboxylation of isocyanides with CO₂

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