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Cu-Catalyzed Three-Component Carboamination of Alkenes.

ABSTRACT: Copper-catalyzed intermolecular carboamination of alkenes with α-halocarbonyls and amines is presented with 42 examples. Electron rich, electron poor, and internal styrenes, as well as α-olefins, are functionalized with α-halocarbonyls and aryl or aliphatic amines. Mechanistic investigations suggest the reaction is proceeding through addition of a carbon-centered radical across an olefin followed by oxidation to form a 5-membered oxocarbenium intermediate and subsequent nucleophilic ring opening to forge the C-N bond.

SUBMITTER: Gockel SN

PROVIDER: S-EPMC6092015 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Rh(III)-Catalyzed Three-Component <i>Syn</i>-Carboamination of Alkenes Using Arylboronic Acids and Dioxazolones.

Project description:Herein we report a Rh(III)-catalyzed three-component carboamination of alkenes from readily available aryl boronic acids as a carbon source and dioxazolones as nitrogen electrophiles. This protocol provides facile access to valuable amine products including α-amino acid derivatives in good yield and regioselectivity without the need for a directing functionality. A series of experiments suggest a mechanism in which the Rh(III) catalyst undergoes transmetalation with the aryl boronic acid followed by turnover limiting, alkene migratory insertion into the Rh(III)-aryl bond. Subsequently, fast Rh-nitrene formation provides the syn-carboamination product selectively after reductive elimination and proto-demetalation. Importantly, the protocol provides 3-component coupling products in preference to a variety of 2-component undesired by-products.

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Oxidative Three-Component Carboamination of Vinylarenes with Alkylboronic Acids.

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