Catalytic and Enantioselective Synthesis of Inherently Chiral Saddle‐Shaped Compounds by [2 + 2 + 2] Cycloaddition of 1,8‐Naphthylene‐Based 1,10‐Diynes with Alkynoates

Abstract In this paper, we describe a chiral Rh‐catalyzed [2 + 2 + 2] cycloaddition of 1,8‐naphthylene‐based 1,10‐diynes of an anti / syn mixture with alkynoates. Thermodynamically stable saddle‐shaped chiral cycloadducts were obtained in good‐to‐high yields and enantiomeric ratios. Hetero [2 + 2 + 2] cycloaddition using aryl cyanides also proceeded to give the corresponding inherently chiral pyridine‐containing compounds.