Chapter 2 The synthesis of chiral sulfoxides through nucleophilic displacement at sulfur

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Publisher Summary This chapter presents the development of chiral sulfoxide synthesis through nucleophilic displacement at sulfur from the pioneering work of Andersen in 1962 to more recent methods. The Andersen procedure for the synthesis of enantiomerically enriched, chiral sulfoxides is discussed in the chapter, followed by the adaptation of the Andersen procedure. The key step in Andersen's procedure involved the preparation of a diastereoisomerically pure sulfinate ester. To date, the main route for large-scale preparation of either enantiomer of nonracemic sulfoxides of type Ar—S(O)—R, where R is introduced using organometallic chemistry, remains the Andersen procedure. Johnson was able to overcome the synthetic limitations of the Andersen procedure by inducing the displacement of aryl groups from diaryl or alkyl aryl sulfoxides with either alkyllithium or alkyl sodium reagents as a general approach to optically active, unsymmetrical dialkyl sulfoxides. The chapter also discusses the application of chiral sulfinamides, chiral cyclic sulfinamides, and chiral cyclic sulfites.