Umpolung of Hemiaminals: Titanocene‐Catalyzed Dehydroxylative Radical Coupling Reactions with Activated Alkenes

Radical measures: A radical coupling reaction, which is proposed to proceed through in situ chlorination of a hydroxy group by Me3SiCl, is used to form quaternary carbon centers with amino groups in α position. The reaction can be scaled up and is used in an efficient six-step total synthesis of (±)-9,10-diepi-stemoamide (see scheme, Cp=cyclopentadienyl, EWG=electron-withdrawing group). As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. 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.