- Access to Optically Active 7-Membered Rings by a 2-Step Synthetic Sequence: Cu-Catalyzed Stereoselective Cyclopropanation of Branched 1,3-Dienes/Rh-Catalyzed Stereoconvergent [5+2] Cycloaddition
Michele Garbo, Céline Besnard, Laure Guénée, Clément Mazet*
ACS Catal. 2020, 10, 9604-9611
We report a 2-step cyclopropanation/cycloaddition catalytic sequence that provides access to optically active 7-membered rings with a carboxyl-bearing tertiary stereocenter. In the first step, the Cu-catalyzed cyclopropanation of branched dienes generates vinylcyclopropanes in high yield, regioselectivity and enantioselectivity albeit in modest cis/trans diastereoselectivity. The stereoconvergent nature of the subsequent Rh-catalyzed [5+2] cycloaddition with alkynes overrides this apparent limitation and affords preferentially one 7-membered ring out of the 8 or 16 possible stereoisomers that can be theoretically generated. The final regioselectivity and enantioselectivity are high in the majority of cases. The method is versatile and tolerates a broad range of functional groups.
open archive unige:140183
Editor’s version DOI: 10.1021/acscatal.0c02956
Dataset DOI: 10.26037/yareta:oe2busam7ncozaiwfd5wvoozzm