Journal
JACS AU
Volume 2, Issue 3, Pages 745-761Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacsau.2c00014
Keywords
aldehyde deformylations; metal-dioxygen complexes; aldehyde deformylation mechanism; inner-sphere mechanism; homolytic aldehyde C-C bond cleavage; dioxygen O-O bond cleavage; DFT mechanistic study
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Funding
- National Science Foundation of China [22173103, 21773240]
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The study investigated the inner-sphere mechanism of aldehyde deformylations using density functional theory (DFT) and discovered a unique reaction pathway, offering a new perspective to understand relevant biological processes and discover metal-dioxygen catalysts for aerobic transformations.
Aldehyde deformylations occurring in organisms are catalyzed by metalloenzymes through metal-dioxygen active cores, attracting great interest to study small-molecule metal-dioxygen complexes for understanding relevant biological processes and developing biomimetic catalysts for aerobic transformations. As the known deformylation mechanisms, including nucleophilic attack, aldehyde alpha-H-atom abstraction, and aldehyde hydrogen atom abstraction, undergo outer-sphere pathways, we herein report a distinct inner-sphere mechanism based on density functional theory (DFT) mechanistic studies of aldehyde deformylations with a copper (10-superoxo complex. The inner-sphere mechanism proceeds via a sequence mainly including aldehyde end-on coordination, homolytic aldehyde C-C bond cleavage, and dioxygen O-O bond cleavage, among which the C-C bond cleavage is the rate-determining step with a barrier substantially lower than those of outer-sphere pathways. The aldehyde C-C bond cleavage, enabled through the activation of the dioxygen ligand radical in a second-order nucleophilic substitution (S(N)2)-like fashion, leads to an alkyl radical and facilitates the subsequent dioxygen O-O bond cleavage. Furthermore, we deduced the rules for the reactions of metal-dioxygen complexes with aldehydes and nitriles via the inner-sphere mechanism. Expectedly, our proposed inner-sphere mechanisms and the reaction rules offer another perspective to understand relevant biological processes involving metal-dioxygen cores and to discover metal-dioxygen catalysts for aerobic transformations.
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