Dataset Information

Homologation of Electron-Rich Benzyl Bromide Derivatives via Diazo C-C Bond Insertion.

ABSTRACT: The ability to manipulate C-C bonds for selective chemical transformations is challenging and represents a growing area of research. Here, we report a formal insertion of diazo compounds into the "unactivated" C-C bond of benzyl bromide derivatives catalyzed by a simple Lewis acid. The homologation reaction proceeds via the intermediacy of a phenonium ion, and the products contain benzylic quaternary centers and an alkyl bromide amenable to further derivatization. Computational analysis provides critical insight into the reaction mechanism, in particular the key selectivity-determining step.

SUBMITTER: Modak A

PROVIDER: S-EPMC8755606 | biostudies-literature | 2022 Jan

REPOSITORIES: biostudies-literature

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Homologation of Electron-Rich Benzyl Bromide Derivatives via Diazo C-C Bond Insertion.

Modak Atanu A Alegre-Requena Juan V JV de Lescure Louis L Rynders Kathryn J KJ Paton Robert S RS Race Nicholas J NJ

Journal of the American Chemical Society 20211213 1

The ability to manipulate C-C bonds for selective chemical transformations is challenging and represents a growing area of research. Here, we report a formal insertion of diazo compounds into the "unactivated" C-C bond of benzyl bromide derivatives catalyzed by a simple Lewis acid. The homologation reaction proceeds via the intermediacy of a phenonium ion, and the products contain benzylic quaternary centers and an alkyl bromide amenable to further derivatization. Computational analysis provides ...[more]

PMID: 34898193

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Project description:Recently, noncovalent interactions in complexes and crystals have attracted considerable interest. The current study was thus designed to gain a better understanding of three seminal types of noncovalent interactions, namely: hydrogen, halogen and tetrel interactions with π-systems. This study was performed on three models of Lewis acids: X3-C-H, F3-C-X and F-T-F3 (where X = F, Cl, Br and I; and T = C, Si, Ge and Sn) and three π-systems as Lewis bases: benzene (BZN), 1,3,5-trifluorobenzene (TFB) and hexafluorobenzene (HFB). Quantum mechanical calculations, including geometrical optimization, molecular electrostatic potential (MEP), maximum positive electrostatic potential (V s,max), Point-of-Charge (PoC), potential energy surface (PES), quantum theory of atoms in molecules (QTAIM) and noncovalent interaction (NCI) calculations, were carried out at the MP2/aug cc-pVDZ level of theory. The binding energies were additionally benchmarked at the CCSD(T)/CBS level. The results showed that: (i) the binding energies of the X3-C-H⋯π-system complexes were unexpectedly inversely correlated with the V s,max values on the hydrogen atom but directly correlated with the X atomic sizes; (ii) the binding energies for the F3-C-X⋯π-system and F-T-F3⋯π-system complexes were correlated with the σ-hole magnitudes of the X and T atoms, respectively; and (iii) for the F3-C-F⋯π-system complexes, the binding energy was as strong as the π-system was electron-deficient, indicating the dominating nucleophilic character of the fluorine atom. NCI analysis showed that the unexpected trend of X3-C-H⋯π-system binding energies could be attributed to additional attractive interactions between the X atoms in the X3-C-H molecule and the carbon atoms of the π-system. Furthermore, the I3-Sn-H molecule was employed as a case study of hydrogen, halogen and tetrel interactions with π-systems. It was found that hydrogen and halogen interactions of the I3-Sn-H molecule correlated with the electron-richness of the π-system. In contrast, tetrel interactions correlated with the electron deficiency of the π-system.

Dataset Information

Homologation of Electron-Rich Benzyl Bromide Derivatives via Diazo C-C Bond Insertion.

Publications

Homologation of Electron-Rich Benzyl Bromide Derivatives via Diazo C-C Bond Insertion.

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