Visible‐Light‐Driven Four‐Component Radical Relay Aminocarbonylation of Unactivated Alkenes^†

Abstract

Comprehensive SummaryCatalytic four‐component radical carbonylation of unactivated alkenes has recently been recognized as a robust protocol for rapid construction of various structurally diverse carbonyl compounds. Given the significance of fluorine‐containing groups, this reaction class has been extensively applied to assembly of a variety of perfluoroalkyl carboxylic acid derivatives by transition metal catalysis. Herein, we report a visible‐light‐driven radical relay 1,2‐perfluoroalkylation aminocarbonylation of unactivated alkenes using CO gas as carbonyl source and 4CzIPN as organic photocatalyst. A wide range of alkenes and amines were well tolerated, providing the valuable β‐perfluoroalkylated amides with generally good yields and high chemoselectivity.

Palladium-catalyzed multi-component Heck alkynylcarbonylation of unactivated alkenes for synthesis of β,γ-alkynoates

“…5 This extremely limited reaction selectivity highlights the universal challenges limiting the development of multi-component carbonylation reactions, which can be summarised as follows: (1) prioritising CO coordination with C–Pd( ii )–X species over that of alkenes; (2) developing a catalyst system that can delicately mediate the selective incorporation of alkenes in the presence of alkenes and CO; and (3) orchestrating an inter-molecular, chemoselective four-component carbonylation reaction, which typically forms several by-products. At present, there are two ways to temporarily avoid these challenges: (1) performing the Pd-catalysed multi-component carbonylation reaction of alkyl halides using carbon radicals as a trigger 6 and (2) using a bi-metallic catalysis pathway (Scheme 1B). 7 In addition, the priority binding of olefins instead of CO to C–Pd( ii )–X species can be accomplished via the Pd-catalysed intra-molecular Heck cyclisation–carbonylation reaction; however, this reaction usually realises intra-molecular transformations.…”