Synthesis, Table of Contents Synthesis 2015; 47(14): 2113-2124DOI: 10.1055/s-0034-1379914 paper © Georg Thieme Verlag Stuttgart · New York Phosphine Oxide Catalyzed, Tetrachlorosilane-Mediated Enantioselective Direct Aldol Reactions of Thioesters Sergio Rossi* Dipartimento di Chimica, Universita degli Studi di Milano, via Golgi 19, 20133 Milano, Italy Email: sergio.rossi@unimi.it , Rita Annunziata Dipartimento di Chimica, Universita degli Studi di Milano, via Golgi 19, 20133 Milano, Italy Email: sergio.rossi@unimi.it , Franco Cozzi Dipartimento di Chimica, Universita degli Studi di Milano, via Golgi 19, 20133 Milano, Italy Email: sergio.rossi@unimi.it , Laura Maria Raimondi Dipartimento di Chimica, Universita degli Studi di Milano, via Golgi 19, 20133 Milano, Italy Email: sergio.rossi@unimi.it › Author Affiliations Recommend Article Abstract Buy Article All articles of this category Abstract The stereoselective direct aldol reaction of S-phenyl thioesters and aromatic aldehydes promoted by tetrachlorosilane was realized for the first time; the proposed mechanism involves the formation of a chiral cationic hypervalent silicon species and requires the presence of catalytic amounts of a Lewis base, like a chiral phosphine oxide. The reaction affords syn β-hydroxy thioesters as major isomers in good yields, high diastereoselectivity (up to 99:1), and up to 92% enantiomeric excess. The absolute configuration of the major isomer was established by converting the product into the corresponding β-hydroxy ester. The scope of the reaction was also investigated by employing differently substituted thioesters in combination with different aromatic aldehydes. Key words Key wordsasymmetric catalysis - direct aldol reaction - hypercoordinate silicon - phosphine oxides - thioesters Full Text References References 1a Denmark SE, Beutner GL. Angew. Chem. Int. Ed. 2008; 47: 1560 1b Kotani S, Sugiura M, Nakajima M. Chem. Rec. 2013; 13: 362 1c Rossi S, Benaglia M, Genoni A. Tetrahedron 2014; 70: 2065 1d Benaglia M, Guizzetti S, Rossi S In Catalytic Methods in Asymmetric Synthesis . Gruttadauria M, Giacalone F. Wiley-VCH; Weinheim: 2011: 579-624 2a Tandura S, Voronkov M, Alekseev N. Top. Curr. Chem. 1985; 131: 99 2b Corriu RJ. 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