The 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 Et3 B/air.

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Recent progress in the nitroso-ene reaction indicates the potentially rich reactivity of the nitroso species. In this study, we highlight the synthetic efforts towards the construction of the aza-spirocyclic or aza-bridged ring embedded in biologically significant alkaloids via the proposed approach. Our endeavors along this direction are exemplified in the formal synthesis of (±)-cephalotaxine and the total synthesis of (-)-hosieine A. 1 Introduction 2 Aza-Spirocyclane: A Formal Synthesis of (±)-Cephalotaxine 3Method Development 4Aza-Bridge Ring: A Total Synthesis of (-)-Hosieine A 5 Epilogue

The first total synthesis of (À)-hosieine Aw as 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.A lso noteworthy is the retention of stereochemistry at C9 in the facile radical debromination initiated by Et 3 B/air.