Enantioselective Conjugate Additions of “Difficult” Ketones to Nitrodienynes and Tandem Annulations

The first enantioselective conjugate additions of problematic aromatic ketones and acetone to nitrodienynes have been achieved by employing a chiral multifunctional primary amine catalyst recently developed by us. The reactions took place in a 1,4‐manner. Furthermore, by utilizing the resulting chiral functionalized 1,3‐enynes as a starting point, we have developed unprecedented p ‐toluenesulfonic acid‐catalyzed tandem annulations, which allow the efficient and selective construction of various synthetically useful cyclic 1,5‐diketones (R=Ar) and dienones (R=Me).