Bioinspired, Base- and Metal-Free, Mild Decarboxylative Aldol Activation of Malonic Acid Half Thioesters Under Phase-Transfer Reaction Conditions

Utilizing ‘off the shelf’ commercially available, cheap, small synthetic molecules that mimic the efficient mediation of important bioreactions utilized by Nature is not only highly sought after but also currently highly topical. This paper details our preliminary efforts at developing a unique base...

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Bibliographic Details
Published in:Advanced synthesis & catalysis 2015-04, Vol.357 (6), p.1245-1257
Main Authors: Bew, Sean P., Stephenson, G. Richard, Rouden, Jacques, Ashford, Polly-Anna, Bourane, Manuel, Charvet, Agathe, Dalstein, Virginie M. D., Jauseau, Raphael, Hiatt-Gipson, G. D., Martinez-Lozano, Luis A.
Format: Article
Language:English
Subjects:
Activation
Aldehydes
aldol reaction
Arrays
base-free conditions
Chemical Sciences
Chlorine
decarboxylation
Inert
Mediation
metal-free conditions
phase-transfer process
Synthesis
Thioesters
Utilities
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Summary:Utilizing ‘off the shelf’ commercially available, cheap, small synthetic molecules that mimic the efficient mediation of important bioreactions utilized by Nature is not only highly sought after but also currently highly topical. This paper details our preliminary efforts at developing a unique base‐ and metal‐free phase‐transfer‐mediated malonic acid thioester (MAHT) ‘activation protocol’ that efficiently generates (±)‐β‐thioesters. Our bioinspired aldol process is exceptionally mild, conducted under near neutral pH reaction conditions, does not require an inert, oxygen‐free atmosphere or anhydrous reaction conditions and is highly atom‐economic. Exemplifying the utility of our protocol, the synthesis of an array of structurally and functionally diverse (±)‐β‐hydroxy thioesters equipped with highly prized functionality, i.e., chlorine, bromine, fluorine, nitrile and nitro groups, is reported, as is the diastereoselective potential of this important reaction.
ISSN:1615-4150
1615-4169
DOI:10.1002/adsc.201400915