Direct C-H ?-Arylation of Enones with ArI(O2CR)2 Reagents.

ABSTRACT: ?-Arylation of ?,?-unsaturated ketones constitutes a powerful synthetic transformation. It is most commonly achieved via cross-coupling of ?-haloenones, but this stepwise strategy requires prefunctionalized substrates and expensive catalysts. Direct enone C-H ?-arylation would offer an atom- and step-economical alternative, but such reports are scarce. Herein we report the metal-free direct C-H arylation of enones mediated by hypervalent iodine reagents. The reaction proceeds via a reductive iodonium Claisen rearrangement of in situ-generated ?-pyridinium silyl enol ethers. The aryl groups are derived from ArI(O2CCF3)2 reagents, which are readily accessed from the parent iodoarenes. The reaction is tolerant of a wide range of substitution patterns, and the incorporated arenes maintain the valuable iodine functional handle. Mechanistic investigations implicate arylation via an umpoled "enolonium" species and show that the presence of a ?-pyridinium moiety is critical for the desired C-C bond formation.

SUBMITTER: Sousa E Silva FC 

PROVIDER: S-EPMC7067356 | biostudies-literature | 2020 Jan

REPOSITORIES: biostudies-literature