Synthesis of 2‐Substituted Bicyclo[2.1.1]hexan‐1‐ols via SmI<sub>2</sub>‐Mediated Reductive Cyclization Reactions

The replacement of benzene rings with saturated bioisosteric counterparts is a key priority in drug discovery programs, and disubstituted bicyclo[2.1.1]hexanes have been recognized as flexible molecular scaffolds that could act as <i>ortho</i>‐substituted benzene bioisosteres. In this study, we outline the synthesis of a wide range of 2‐substituted bicyclo[2.1.1]hexan‐1‐ols, which have the potential to emulate <i>ortho</i>‐phenolic derivatives, via SmI₂‐mediated reductive cyclization reactions. The synthetic utility of this methodology was exemplified by the preparation of several saturated analogs of pharmaceutically relevant compounds.