Reversible Homolysis of a Carbon-Carbon σ-Bond Enabled by Complexation-Induced Bond-Weakening.
| Autor: | Kim S; Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States., Chen PP; Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States., Houk KN; Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States., Knowles RR; Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States. |
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| Jazyk: | angličtina |
| Zdroj: | Journal of the American Chemical Society [J Am Chem Soc] 2022 Aug 31; Vol. 144 (34), pp. 15488-15496. Date of Electronic Publication: 2022 Aug 22. |
| DOI: | 10.1021/jacs.2c01229 |
| Abstrakt: | A case study of catalytic carbon-carbon σ-bond homolysis is presented. The coordination of a redox-active Lewis acid catalyst reduces the bond-dissociation free energies of adjacent carbon-carbon σ-bonds, and this complexation-induced bond-weakening is used to effect reversible carbon-carbon bond homolysis. Stereochemical isomerization of 1,2-disubstituted cyclopropanes was investigated as a model reaction with a ruthenium (III/II) redox couple adopted for bond weakening. Results from our mechanistic investigation into the stereospecificity of the isomerization reaction are consistent with selective complexation-induced carbon-carbon bond homolysis. The Δ G ‡ of catalyzed and uncatalyzed reactions were estimated to be 14.4 and 40.0 kcal/mol, respectively with the computational method, (U)PBE0-D3/def2-TZVPP-SMD(toluene)//(U)B3LYP-D3/def2-SVP. We report this work as the first catalytic example where the complexation-induced bond-weakening effect is quantified through transition state analysis. |
| Databáze: | MEDLINE |
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