Overlooked aza-S(iv) motifs: synthesis and transformations of sulfinamidines and sulfinimidate esters

Abstract

Significant advancements have recently been made in the chemistry of sulfinamidines and sulfinimidate esters. This review aims to provide an overview of the synthetic methods for the preparation and transformation of these overlooked compounds.

N,N’‐Diaryl‐Sulfurdiimides are Strongly Redox Tuned

“…The UV-vis absorption spectra of the intensely coloured aryl SDIs 1-9 were measured as solutions in CH 2 Cl 2 (Figure 8a). [64] These are strong chromophores, with absorption coefficients ranging from 3600 (9) to almost 15000 L • mol À 1 • cm À 1 (1). Of particular interest to this study was the observation of distinct variations in the principal absorption maxima, λ 1 and λ 2 , in the visible region.…”

“…[1,7] The organic chemistry of SDIs has been reviewed repeatedly, [8] and has recently been revived intensively due to significant advances in pharmaceutical applications. [9] A reliable thermodynamic scale has been developed for the replacement of the SO bonds in SO 2 with SNR groups. [10] The nature of the NS bonds in SDIs has been discussed in great depth [11] but is now definitively confirmed to be of the heteroallylic nature shown at the bottom of Figure 1; [11b] in graphical schemes the shorthand partially dashed double line notation has been adopted, but in text, whether written NSN or À NSNÀ , this heteroallylic character will always be intended.…”

Azasulfur(iv) derivatives of sulfite and sulfinate esters by formal S–S bond insertion of dichloramines

“…6 a ,8 d ,20 d ,21 Such compounds are stable, but little-described, and their facile preparation from commercial starting materials contrasts the typical routes to, for example, sulfinimidates, which commonly start from pre-synthesized sulfenamides or sulfinylamines. 22 A variety of these SN derivatives is prepared to explore the synthetic breadth of these functional groups. Ultimately, we demonstrate how azasulfur( iv ) compounds can serve as a strategic choice for platform chemicals, enabling access to all classes of heteroatom-attached azasulfur( vi ) species.…”