Vinyl Cation Stabilization by Silicon Enables a Formal Metal‐Free α‐Arylation of Alkyl Ketones. Issue 48 (22nd October 2019)

• Record Type: Journal Article
• Authors: Pons, Amandine; Michalland, Jean; Zawodny, Wojciech; Chen, Yong; Tona, Veronica; Maulide, Nuno
• Is Part Of: Angewandte Chemie international edition. Volume 58:Issue 48(2019)
• Page Start: 17303
• Page End: 17306
• Publication Date: 2019-10-22
• Subjects: α-arylation -- sigmatropic rearrangement -- silicon β-effect -- vinyl cations; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201909381
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The ability of silicon to stabilize vinyl cationic species leads to a redox arylation of alkynes whereby the stringent limitations of reactivity and regioselectivity of alkyl‐substituted alkynes are lifted. This allows the synthesis of a range of α‐silyl‐α′‐arylketones under mild conditions in good to excellent yields and with high functional group tolerance, whereby the silicon moiety in the final products can either be removed for a formal acetone monoarylation transform, or capitalized upon for subsequent electrophilic substitutions at either side of the carbonyl group. Abstract : I can Si clearly now : The ability of silicon to stabilize vinyl cationic species enables a redox arylation of alkynes whereby the poor reactivity and regioselectivity of alkyl‐substituted alkynes are lifted. This enables the synthesis of a range of α‐silyl‐α′‐arylketones under mild conditions in good to excellent yields. The silicon moiety of the products can either be removed or harnessed for additional C−C bond formation.