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Synthesis of Monothiomalonates – Versatile Thioester Enolate Equivalents for C–C Bond Formations
Author(s) -
Engl Oliver D.,
Saadi Jakub,
Cosimi Elena,
Wennemers Helma
Publication year - 2017
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.201700196
Subject(s) - thioester , chemistry , substituent , electrophile , alkylation , nucleophile , double bond , ring (chemistry) , alkyl , stereochemistry , aldol reaction , stereoselectivity , malonic acid , combinatorial chemistry , organic chemistry , catalysis , enzyme
Monothiomalonates ( MTM s) are surrogates of thioester enolates that allow for stereoselective C–C bond formations under mild conditions and thereby afford access to synthetically versatile thioester derivatives. Here we present a straightforward synthetic route to MTM s that proceeds through nucleophilic ring‐opening of Meldrum 's acid derivatives followed by O‐alkylation of the resulting malonic acid half thioesters with alkyl triflates or acetimidates as electrophiles. The method affords MTM s in overall yields of 34 – 92% and allows for variations of the oxo‐ and thioester moieties as well as the substituent at the C( α ) position.