Asymmetric, Stereodivergent Synthesis of (−)-Clusianone Utilizing a Biomimetic Cationic Cyclization†
Jonathan H. Boyce
Department of Chemistry, Center for Chemical Methodology and Library Development (CMLD-BU), Boston University, 590 Commonwealth Avenue, Boston, MA 02215 (USA)
Search for more papers by this authorCorresponding Author
Prof. Dr. John A. Porco Jr.
Department of Chemistry, Center for Chemical Methodology and Library Development (CMLD-BU), Boston University, 590 Commonwealth Avenue, Boston, MA 02215 (USA)
Department of Chemistry, Center for Chemical Methodology and Library Development (CMLD-BU), Boston University, 590 Commonwealth Avenue, Boston, MA 02215 (USA)Search for more papers by this authorJonathan H. Boyce
Department of Chemistry, Center for Chemical Methodology and Library Development (CMLD-BU), Boston University, 590 Commonwealth Avenue, Boston, MA 02215 (USA)
Search for more papers by this authorCorresponding Author
Prof. Dr. John A. Porco Jr.
Department of Chemistry, Center for Chemical Methodology and Library Development (CMLD-BU), Boston University, 590 Commonwealth Avenue, Boston, MA 02215 (USA)
Department of Chemistry, Center for Chemical Methodology and Library Development (CMLD-BU), Boston University, 590 Commonwealth Avenue, Boston, MA 02215 (USA)Search for more papers by this authorFinancial support from the National Institutes of Health (R01 GM-073855 and GM-099920) is gratefully acknowledged. We thank Prof. John Snyder, Dr. Paul Ralifo, and Neil Lajkiewicz (Boston University) for helpful discussions and Madeline Weber, Dr. Alexander Grenning, Dr. Munmun Mukerjee, and Scott Pardo (Boston University) for experimental assistance.
Abstract
We report a stereodivergent, asymmetric total synthesis of (−)-clusianone in six steps from commercial materials. We implement a challenging cationic cyclization forging a bond between two sterically encumbered quaternary carbon atoms. Mechanistic studies point to the unique ability of formic acid to mediate the cyclization forming the clusianone framework.
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