Asymmetric Total Synthesis of (+)‐ and (−)‐Myrioneurinol Employing a “Resolutive” Late‐Stage Barton‐McCombie Deoxygenation

Abstract The so‐called Barton‐McCombie reaction is a transformation commonly used in organic synthesis for promoting deoxygenation of alcohols. Almost 50 years after its discovery, this reaction has become a powerful tool for organic chemists due to its wide range of applicability and functional group tolerance, which allows, with high level of anticipation, its incorporation into complex synthetic routes such as the ones aiming at the total synthesis of natural products. In this article, we describe the first example of a resolutive version of this reaction by using a chiral chlorothionoformate as the activating reagent, and its related strategic potential through a late‐stage application to the total synthesis of both enantiomers of myrioneurinol, a complex tetracyclic alkaloid featuring 5 contiguous stereogenic centers.