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Chem Soc Rev. 2018 Feb 21;47(4):1307-1350. doi: 10.1039/c6cs00703a. Epub 2017 Dec 22.

Chiral sulfoxides: advances in asymmetric synthesis and problems with the accurate determination of the stereochemical outcome.

Author information

1
School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Nanjing University, 210093 Nanjing, China. hanjl@nju.edu.cn.
2
Department of Organic Chemistry I, Faculty of Chemistry, University of the Basque Country UPV/EHU, Paseo Manuel Lardizábal 3, 20018 San Sebastián, Spain. vadym.soloshonok@ehu.es and IKERBASQUE, Basque Foundation for Science, Alameda Urquijo 36-5, Plaza Bizkaia, 48011 Bilbao, Spain.
3
Molecular Structure Analysis, German Cancer Research Center (DKFZ), Im Neuenheimer Feld 280, D-69009 Heidelberg, Germany. k.klika@dkfz.de.
4
Department of Heterooganic Chemistry, Center of Molecular and Macromolecular Studies, Polish Academy of Sciences, Sienkiewicza 112, 90-363 Łódź, Poland and Institute of Chemistry, Environmental Protection and Biotechnology, Jan Długosz University in Częstochowa, Armii Krajowej 13/15, 42-201 Częstochowa, Poland.
5
Department of Organic Chemistry I, Faculty of Chemistry, University of the Basque Country UPV/EHU, Paseo Manuel Lardizábal 3, 20018 San Sebastián, Spain. vadym.soloshonok@ehu.es and Institute of Chemistry, Jan Kochanowski University in Kielce, Swiętokrzyska 15G, 25-406 Kielce, Poland. alicja.wzorek@ujk.edu.pl.

Abstract

Chiral sulfoxides are in extremely high demand in nearly every sector of the chemical industry concerned with the design and development of new synthetic reagents, drugs, and functional materials. The primary objective of this review is to update readers on the latest developments from the past five years (2011-2016) in the preparation of optically active sulfoxides. Methodologies covered include catalytic asymmetric sulfoxidation using either chemical, enzymatic, or hybrid biocatalytic means; kinetic resolution involving oxidation to sulfones, reduction to sulfides, modification of side chains, and imidation to sulfoximines; as well as various other methods including nucleophilic displacement at the sulfur atom for the desymmetrization of achiral sulfoxides, enantioselective recognition and separation based on either metal-organic frameworks (MOF's) or host-guest chemistry, and the Horner-Wadsworth-Emmons reaction. A second goal of this work concerns a critical discussion of the problem of the accurate determination of the stereochemical outcome of a reaction due to the self-disproportionation of enantiomers (SDE) phenomenon, particularly as it relates to chiral sulfoxides. The SDE is a little-appreciated phenomenon that can readily and spontaneously occur for scalemic samples when subjected to practically any physicochemical process. It has now been unequivocally demonstrated that ignorance in the SDE phenomenon inevitably leads to erroneous interpretation of the stereochemical outcome of catalytic enantioselective reactions, in particular, for the synthesis of chiral sulfoxides. It is hoped that this two-pronged approach to covering the chemistry of chiral sulfoxides will be appealing, engaging, and motivating for current research-active authors to respond to in their future publications in this exciting area of current research.

PMID:
29271432
DOI:
10.1039/c6cs00703a

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