Enantio- and Diastereoselective Addition of TosMIC to Ketones

Abdul Raheem Keeri,^ab Andrea Gualandi,^a Andrea Mazzanti,^c Janusz Lewiński,^b Pier Giorgio Cozzi^a

^a Dipartimento di Chimica “G: Ciamician”, Università di Bologna, Via Selmi 2, 40126, Bologna, Italy
^b Faculty of Chemistry, Warsaw University of Technology, Noakowskiego 3, 00-664, Warsaw, Poland
^c Dipartimento di Chimica “Toso Montanari”, Università di Bologna, Viale del Risorgimento 4, 40136, Bologna, Italy

DOI: 10.1002/chem.201504362.
First published online 23 Nov 2015.

The first catalytic asymmetric addition of TosMIC to unactivated ketones is presented. A combination of Me₂Zn and aminoalcohol catalyst promoted the aldol addition/cyclization reaction to render oxazolines possessing a fully substituted stereocenter with excellent yields (up to 92%), high enantioselectivities (up to 96%), and complete diastereoselectivity. The chiral oxazolines were then used to give, after a straightforward acid hydrolysis, enantioenriched building blocks bearing tertiary alcohol motifs such as hydroxylaldehydes, hydroxylacids, and hydroxylesters without racemization.

Paper on the Wiley Online Library website