Abstract

AbstractThe first total synthesis of (−)‐hosieine A was accomplished and features an unprecedented nitroso–ene cyclization to construct the 2‐azabicyclo[3.2.1]octane ring system. Phosphine‐enabled stereoselective bromohydrination provided interesting mechanistic insights into the anti‐Markovnikov process. Also noteworthy is the retention of stereochemistry at C9 in the facile radical debromination initiated by Et3B/air.

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