Formal Synthesis of (−)‐Aphanorphine Using Sequential Photomediated Radical Reactions of Dithiocarbamates

Abstract

Time to change the light bulb: An alkyl dithiocarbamate, itself formed through a photoinitiated group-transfer cyclization of a carbamoyl radical, undergoes a second photomediated radical process initiated with a different light source. These two reactions, which proceed through the same cyclohexenyl radical intermediate, are key steps in a new asymmetric synthesis of the alkaloid aphanorphine. TEMPO=2,2,6,6-tetramethyl-1-piperidinoxyl radical. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2007/z701055_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.