Concise Total Synthesis of (+)-Bionectins A and C

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 -β-hydroxytryptophan amino acid synthesis, an intramolecular Friedel-Crafts reaction of a silyl-tethered indole, and a new mercaptan reagent...

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Bibliographic Details
Published in:Chemical science (Cambridge) 2013-08, Vol.4 (8), p.3191-3197
Main Authors: Coste, Alexis, Kim, Justin, Adams, Timothy C, Movassaghi, Mohammad
Format: Article
Language:English
Subjects:
Amino acids
Friedel-Crafts reaction
Hydroxylation
Mercaptans
Parents
Synthesis
Synthesis (chemistry)
X-rays
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Summary: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 -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 -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.
ISSN:2041-6520
2041-6539
DOI:10.1039/c3sc51150b