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Vinyl sulfones and sulfonamides are valued for their use as electrophilic warheads in covalent protein inhibitors. Conversely, the S(VI) aza-isosteres thereof, vinyl sulfoximines and sulfonimidamides, are far less studied and have yet to be applied to the field of protein bioconjugation. Herein, we report a range of different synthetic methodologies for constructing vinyl sulfoximine and vinyl sulfonimidamide architectures that allows access to new areas of electrophilic chemical space. We demonstrate how late stage functionalization can be applied to these motifs to incorporate alkyne tags, generating fully functionalized probes for future chemical biology applications. Finally, we establish a workflow for determining the absolute configuration of enantioenriched vinyl sulfoximines and sulfonimidamides by comparing experimentally and computationally determined electronic circular dichroism spectra, enabling access to configurationally assigned enantiomeric pairs by separation.

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It is well known that mounting large-scale productions at the Paris Opéra during the 1830s and 1840s was a highly collaborative effort. The nature of so-called ‘grand opera’ demanded that composer, librettist and stage designer work closely together for the sake of a creation larger than the sum of its parts. Above them loomed the directeur, who laboured to ensure that his creative team had the means to produce their æuvres both in materials and human resources, and to guarantee that the Opéra made a profit from the finished products. A fifth collaborator, the singer, is not often cited as such in the literature, but in many ways wielded the greatest power in the creation of Parisian operatic works. By the 1830s, European singers had achieved professional status, and a singing artist of high calibre could find the Opéra a perfect venue in which to flex muscle. During the Opera's ‘golden age’, a bourgeois public, tired of political upheaval and economic uncertainty, found escape in the new ‘romanticè fare of the Opéra, and elevated the singers who strode its boards to what today is called ‘star status’. The Opéra became a temple and its singers, adored gods and goddesses. A beloved singer could – and did – ensure an opera's success simply by appearing in it, or doom it to failure by refusing to appear. With such power a singer could easily hold a new opera for ransom, forcing the composer and librettist to revise, excise or otherwise alter the work to some self-serving end. To secure a place for their stage works at the Opéra and to guarantee a public triumph, therefore, it is not surprising that composers such as Donizetti, and especially Meyerbeer, the leading composer of French grand opera, composed or revised their operas for particular singers.