Abstract
Sulfinylamines (R−N=S=O), monoaza analogues of sulfur dioxide, have been known for well over a century, and their reactivity as sulfur electrophiles and in Diels‐Alder reactions is well‐established. However, they have only rarely been used in organic synthesis in recent decades despite the increasing prominence of compounds containing N=S=O functionality, such as sulfoximines and sulfonimidamides. This Minireview aims to bring wider visibility to the unique chemistry enabled by this class of compounds. We focus on advances from the last 10 years, including the first examples of their use in the one‐pot syntheses of sulfoximines and sulfonimidamides. Also covered are the reactions of sulfinylamines with carbon‐centred radicals, their use for formation of heterocycles through cycloadditions, and catalytic enantioselective allylic oxidation of alkenes via a hetero‐ene reaction. These examples highlight the different reactivity modes of sulfinylamines and their underappreciated potential for forming molecules which contain high‐ or low‐valent sulfur, or even no sulfur at all.
Highlights
The surprisingly long history of sulfinylamines began in 1878 when Böttinger discovered that “thionyl chloride acts extremely violently on aniline ... “every drop of the thionyl chloride solution produces a hissing noise”.[1]
This Minireview has described the properties of sulfinylamines and their applications in organic synthesis over the last decade
The discovery that N-sulfinylhydroxylamines (BiPhONSO 16) can function as precursors to highly reactive and electrophilic sulfinyl nitrenes, which has allowed the first one-pot de novo synthesis of sulfoximines,[12] will likely have an impact on the way organosulfur molecules are synthesised in future
Summary
The surprisingly long history of sulfinylamines began in 1878 when Böttinger discovered that “thionyl chloride acts extremely violently on aniline ... “every drop of the thionyl chloride solution produces a hissing noise”.[1]. We could not develop a direct one-pot synthesis of sulfoximines using conventional sulfinylamine reagents such as 5 and 11 These efforts were hindered by the poor reactivity of known sulfur(VI) electrophiles such as sulfonimidoyl chlorides, fluorides and esters with organometallic carbon nucleophiles, which often do not react or undergo reduction to the sulfinamide instead of substitution at sulfur. We found that the O-aryl-N-sulfinylhydroxylamine BiPhONSO (16) combines good stability and a convenient solid form with excellent reactivity.[12] Addition of a Grignard or organolithium reagent to BiPhONSO initially forms an N-aryloxysulfinamide, which loses the phenoxide group to give a sulfinyl nitrene This can react with a second carbon or nitrogen nucleophile to give sulfoximines or sulfonimidamides (Scheme 7). Enantioselective allylic oxidation of unactivated (Z)-alkenes using N-sulfinylsulfonamide 36 and derivatisation of the resulting allyl sulfinamides to diversely substituted chiral products
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
