Concise and Enantioselective Total Synthesis of (−)-Mehranine, (−)-Methylenebismehranine, and Related
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Author(s) • •
Mewald, Marius
Medley, Jonathan William
Movassaghi, Mohammad
Date Issued
October 2014
Journal
Angewandte Chemie International Edition
Publisher
Wiley Blackwell
Citation
Mewald, Marius; Medley, Jonathan William and Movassaghi, Mohammad. “ Concise and Enantioselective Total Synthesis of (−)-Mehranine, (−)-Methylenebismehranine, and Related Aspidosperma Alkaloids .”Angewandte Chemie International Edition 53, 43 (September 2014): 11634–11639 © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Author's final manuscript
Abstract
We report an efficient and highly stereoselective strategy for the synthesis of Aspidosperma alkaloids based on the transannular cyclization of a chiral lactam precursor. Three new stereocenters are formed in this key step with excellent diastereoselectivity due to the conformational bias of the cyclization precursor, leading to a versatile pentacyclic intermediate. A subsequent stereoselective epoxidation followed by a mild formamide reduction enabled the first total synthesis of the Aspidosperma alkaloids (−)-mehranine and (+)-(6S,7S)-dihydroxy-N-methylaspidospermidine. A late-stage dimerization of (−)-mehranine mediated by scandium trifluoromethanesulfonate completed the first total synthesis of (−)-methylenebismehranine.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1002/anie.201405609