American Chemical Society
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Nonenzymatic Acylative Kinetic Resolution of Baylis−Hillman Adducts

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journal contribution
posted on 2007-08-31, 00:00 authored by Ciarán Ó Dálaigh, Stephen J. Connon
The first efficient nonenzymatic acylative kinetic resolution of Baylis−Hillman adducts is reported. Chiral pyridine catalyst 1a and an optimized analogue 1e are capable of promoting the synthetically useful enantioselective acylation (the efficiency of which is outstanding for sp2−sp2 carbinol substrates, s = 3.5−13.1, ee up to 97%) of Baylis−Hillman adducts derived from recalcitrant precursors which are currently difficult to synthesize utilizing benchmark asymmetric Baylis−Hillman reaction catalyst technology. A novel one-pot synthesis−kinetic resolution process involving a DBU-catalyzed Baylis−Hillman reaction and subsequent 1e/DBU-mediated enantioselective acylation has also been developed.