Total synthesis of (+)-herboxidiene/GEX 1A

A total synthesis of (+)-herboxidiene/GEX 1A has been accomplished from (R)- and (S)-lactate esters in a highly efficient manner. Key steps of the synthesis involve substrate-controlled titanium-mediated aldol reactions from chiral lactate-derived ethyl ketones, an oxa-Michael cyclization, an Irelan...

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Bibliographic Details
Published in:Organic & biomolecular chemistry 2017-02, Vol.15 (8), p.1842-1862
Main Authors: Gómez-Palomino, Alejandro, Pellicena, Miquel, Krämer, Katrina, Romea, Pedro, Urpí, Fèlix, Aullón, Gabriel, Padrón, José M
Format: Article
Language:English
Subjects:
Fatty Alcohols - chemical synthesis
Fatty Alcohols - chemistry
Molecular Conformation
Pyrans - chemical synthesis
Pyrans - chemistry
Stereoisomerism
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Summary:A total synthesis of (+)-herboxidiene/GEX 1A has been accomplished from (R)- and (S)-lactate esters in a highly efficient manner. Key steps of the synthesis involve substrate-controlled titanium-mediated aldol reactions from chiral lactate-derived ethyl ketones, an oxa-Michael cyclization, an Ireland-Claisen rearrangement, and a Suzuki coupling. Furthermore, computational studies of the oxa-Michael reaction have unveiled the dramatic influence of intramolecular hydrogen bonds on the stereochemical outcome of such cyclizations, whereas biological analyses have clearly proved the important cytoxicity of (+)-herboxidiene/GEX 1A.
ISSN:1477-0520
1477-0539
DOI:10.1039/c7ob00072c