Enantioselective Cobalt(III)-Catalyzed [4 + 1] Annulation of Benzamides: Cyclopropenes as One-Carbon Synthons

A chiral cyclopentadienyl cobalt(III)-catalyzed enantioselective [4 + 1] annulation of <i>N</i>-chlorobenzamides with cyclopropenes is reported. The cobalt catalyst engages in the C–H activation as well as promotes the C–C bond cleavage of the cyclopropene, rendering it as a one-carbon u...

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Main Author: Lenin Kumar Verdhi (13016115) (author)
Other Authors: Matthew D. Wodrich (1263717) (author), Nicolai Cramer (1516678) (author)
Published: 2025
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Summary:A chiral cyclopentadienyl cobalt(III)-catalyzed enantioselective [4 + 1] annulation of <i>N</i>-chlorobenzamides with cyclopropenes is reported. The cobalt catalyst engages in the C–H activation as well as promotes the C–C bond cleavage of the cyclopropene, rendering it as a one-carbon unit for the annulation. The reaction efficiently constructs biologically relevant chiral isoindolinones with selectivities of up to 99:1 er and >20:1 <i>E</i>/<i>Z</i> ratios. The cobalt(III) catalyst displays a unique orthogonal reactivity profile delivering [4 + 1] annulation products, whereas its rhodium(III) homologue engages in the more classical [4 + 2] annulation pattern. Computational studies reveal the origin of these reactivity divergences.