Concise total synthesis of (+)-bionectins A and C
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Movassaghi_Concise total.pdf
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1.99 MB
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Author(s)
Coste, Alexis
Kim, Justin
Adams, Timothy C.
Movassaghi, Mohammad
Date Issued
May 2013
Journal
Chemical Science
Publisher
Royal Society of Chemistry, The
Citation
Coste, Alexis, Justin Kim, Timothy C. Adams, and Mohammad Movassaghi. “Concise Total Synthesis of (+)-Bionectins A and C.” Chemical Science 4, no. 8 (2013): 3191.
Version
Author's final manuscript
Abstract
The concise and efficient total synthesis of (+)-bionectins A and C is described. Our approach to these natural products features a new and scalable method for erythro-β-hydroxytryptophan amino acid synthesis, an intramolecular Friedel–Crafts reaction of a silyl-tethered indole, and a new mercaptan reagent for epipolythiodiketopiperazine (ETP) synthesis that can be unravelled under very mild conditions. In evaluating the impact of C12-hydroxylation, we have identified a unique need for an intramolecular variant of our Friedel–Crafts indolylation chemistry. Several key discoveries including the first example of permanganate-mediated stereoinvertive hydroxylation of the α-stereocenters of diketopiperazines as well as the first example of a direct triketopiperazine synthesis from a parent cyclo-dipeptide are discussed. Finally, the synthesis of (+)-bionectin A and its unambiguous structural assignment through X-ray analysis provides motivation for the reevaluation of its original characterization data and assignment.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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Creative Commons Attribution-Noncommercial-Share Alike
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DOI of Published Version
https://doi.org/10.1039/c3sc51150b
