A Catalytic, Enantioselective Sulfamate Tethered Aza-Michael Cyclization.

We show the first examples of enantioselective cyclization reactions of tethered sulfamates onto pendant α,β-unsaturated esters, ketones, and thioesters. This reaction is promoted by a new chiral bifunctional guanidine catalyst and is operationally very simple. A variety of primary sulfamates and sulfamides were examined, and in many cases, products were delivered in excellent yields and enantiomeric ratios. With secondary sulfamates, kinetic resolutions were possible. The product oxathiazinanes are very useful chiral synthons.