Asymmetric Morita-Baylis-Hillman reaction of chiral glyoxylates

The first Morita-Baylis-Hillman reaction of chiral glyoxylic acid derivativ es, i.e. N-glyoxyloyl-(2-R)-bornane-10,2-sultam and (-)-8-phenylmenthyl gly oxylate is described. The reaction with cyclic a,p-unsaturated ketones proc eeded under the catalytic influence of dimethyl sulfide in the presence of titanium tetrachloride. The adducts were obtained with very high diastereoi someric excess (over 95% d.e.) and typical yields of 78%. The absolute conf iguration of the newly created stereogenic center was established by X-ray crystallographic analysis. (C) 2001 Elsevier Science Ltd. All rights reserv ed.