Multiple roles of aryloxide leaving groups in enantioselective annulations employing α,β-unsaturated acyl ammonium catalysis.

ABSTRACT: An isothiourea-catalysed Michael addition-annulation process using β-fluoroalkyl-substituted α,β-unsaturated aryl esters and a range of 2-acylbenzazoles is reported for the enantioselective synthesis of dihydropyranone and dihydropyridinone products bearing polyfluorinated stereocenters (29 examples, up to 98% yield, >99 : 1 er). The choice of aryl group of the aryl ester proved essential in determining reaction enantioselectivity and dihydropyranone : dihydropyridinone product selectivity. The aryloxide leaving group is shown to play a number of essential additional roles, operating (i) as a Brønsted base, circumventing the need for an auxiliary base; and (ii) as a Lewis base to catalyse the isomerisation of dihydropyranone products into thermodynamically-favoured dihydropyridinones. Afte

SUBMITTER: Greenhalgh MD 

PROVIDER: S-EPMC5982221 | biostudies-literature | 2018 Jun

REPOSITORIES: biostudies-literature