Enantioselective total synthesis of (-)-deoxoapodine
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nihms904293.pdf
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Accepted version
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Author(s)
Kang, Taek
White, Kolby L.
Mann, Tyler J.
Hoveyda, Amir H.
Movassaghi, Mohammad
Date Issued
September 27, 2017
Journal
Angewandte Chemie International Edition
Publisher
Wiley
Citation
Kang, Taek, et al., "Enantioselective total synthesis of (-)-deoxoapodine." Angewandte Chemie International Edition 56, 44 (Sept. 2017): p. 13857-60 doi 10.1002/anie.201708088 ©2017 Author(s)
Version
Author's final manuscript
Abstract
The first enantioselective total synthesis of (−)-deoxoapodine is described. Our synthesis of this hexacyclic aspidosperma alkaloid includes an efficient molybdenum-catalyzed enantioselective ring-closing metathesis reaction for the desymmetrization of an advanced intermediate that introduces the C5-quaternary stereocenter. After C21-oxygenation, the pentacyclic core was accessed by electrophilic C19-amide activation and transannular spirocyclization. A biogenetically inspired dehydrative C6-etherification reaction proved highly effective to secure the F-ring and the fourth contiguous stereocenter of (−)-deoxoapodine with complete stereochemical control.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1002/anie.201708088
