Unknown

Dataset Information

0

Lewis Acid Catalyzed Transfer Hydromethallylation for the Construction of Quaternary Carbon Centers.

ABSTRACT: The design and gram-scale synthesis of a cyclohexa-1,4-diene-based surrogate of isobutene gas is reported. Using the highly electron-deficient Lewis acid B(C6 F5 )3 , application of this surrogate in the hydromethallylation of electron-rich styrene derivatives provided sterically congested quaternary carbon centers. The reaction proceeds by C(sp3 )-C(sp3 ) bond formation at a tertiary carbenium ion that is generated by alkene protonation. The possibility of two concurrent mechanisms is proposed on the basis of mechanistic experiments using a deuterated surrogate.

SUBMITTER: Walker JCL 

PROVIDER: S-EPMC6856816 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature

Json Xml
altmetric image

Publications

Lewis Acid Catalyzed Transfer Hydromethallylation for the Construction of Quaternary Carbon Centers.

Walker Johannes C L JCL   Oestreich Martin M  

Angewandte Chemie (International ed. in English) 20190912 43

The design and gram-scale synthesis of a cyclohexa-1,4-diene-based surrogate of isobutene gas is reported. Using the highly electron-deficient Lewis acid B(C<sub>6</sub> F<sub>5</sub> )<sub>3</sub> , application of this surrogate in the hydromethallylation of electron-rich styrene derivatives provided sterically congested quaternary carbon centers. The reaction proceeds by C(sp<sup>3</sup> )-C(sp<sup>3</sup> ) bond formation at a tertiary carbenium ion that is generated by alkene protonation. Th  ...[more]

Similar Datasets

Unknown Stereocontrolled alkylative construction of quaternary carbon centers.
| S-EPMC2666470 | biostudies-literature
Unknown Enantioselective construction of all-carbon quaternary centers by branch-selective Pd-catalyzed allyl-allyl cross-coupling.
| S-EPMC3131072 | biostudies-other
Unknown Synthesis of Vicinal Quaternary All-Carbon Centers via Acid-catalyzed Cycloisomerization of Neopentylic Epoxides.
| S-EPMC7115968 | biostudies-literature
Unknown Rhodium-Catalyzed Enantioselective Cycloisomerization to Cyclohexenes Bearing Quaternary Carbon Centers.
| S-EPMC4856524 | biostudies-literature
Unknown Enantioselective photochemistry through Lewis acid-catalyzed triplet energy transfer.
| S-EPMC5501084 | biostudies-literature
Unknown Enantioselective Synthesis of Vicinal All-Carbon Quaternary Centers via Iridium-Catalyzed Allylic Alkylation.
| S-EPMC6033654 | biostudies-literature
Unknown Ligand-enabled γ-C-H olefination and carbonylation: construction of β-quaternary carbon centers.
| S-EPMC4049142 | biostudies-literature
Unknown Chromium-catalyzed para-selective formation of quaternary carbon centers by alkylation of benzamide derivatives.
| S-EPMC6219510 | biostudies-literature
Unknown Ruthenium catalyzed reductive coupling of paraformaldehyde to trifluoromethyl allenes: CF3-bearing all-carbon quaternary centers.
| S-EPMC3779475 | biostudies-literature
Unknown Synthesis of quaternary carbon stereogenic centers through enantioselective Cu-catalyzed allylic substitutions with vinylaluminum reagents.
| S-EPMC2951504 | biostudies-literature