Syntheses and Transformations of Sulfinamides

Abstract

Sulfinamides, especially enantiopure sulfinamides, are widely used in organic and medicinal synthesis. Syntheses and transformations of racemic and enantioenriched sulfinamides have achieved great progress. Especially sulfinamides demonstrate interesting and valuable reactivity, which deserves to be concerned. This review summarizes the latest development in the synthesis and transformation of sulfinamides and will be helpful for future related research.

Nickel-Catalyzed N-Arylation of Sulfinamides: A Comparative Study versus Analogous Sulfonamide Cross-Couplings

“…The formation of these isomers can be interpreted as arising from the interplay of the chiral (enantioenriched) sulfinamido moiety, the chiral (racemic) cage phosphine, and the Ni­( o -tol) groups, whereby hindered Ni–C bond rotation affords diastereomers as is observed crystallographically. We also cannot rule out the existence of cis / trans isomers, which has been observed for ( L1 )­Ni­( o -tol)­Cl) . The presence of this isomeric mixture renders the 1 H, 13 C­{ 1 H}, and 31 P­{ 1 H} NMR spectra sufficiently complex so as to preclude definitive assignment; these spectra are provided in Figures S23–S25 (for C1 ) and Figures S26–S28 (for C2 ) for the sake of completeness.…”

“…The synthesis of substituted sulfinamides represents an area of considerable interest, given the utility of such compounds in synthetic chemistry (e.g., as ammonia surrogates), medicinal chemistry (e.g., bioisosteres of carboxylic acids), and the design of new (chiral) ancillary ligands for use in metal catalysis. However, despite advances in metal-catalyzed C–N cross-coupling methodologies, relatively little progress has been made regarding the development of sulfinamide N-arylations employing (hetero)­aryl (pseudo)­halide electrophiles, with the few examples reported thus far being limited to Pd, , Cu, and Cu/Fe catalyst systems (Figure A).…”

Asymmetric Synthesis of S(IV) and S(VI) Stereogenic Centers

“…These nitrogen atoms provide more interaction sites and additional modification sites. Due to the increased interest in these sulfur stereogenic centers in drug discovery, many strategies have been developed for their synthesis. − However, most reported methodologies are only able to generate racemic products. − …”

Transsulfinamidation of Sulfinamides with Amines

“…Sulfinamides are widely utilized in organic synthesis and medicinal chemistry. For instance, they are useful intermediates in the preparation of various sulfur compounds such as sulfonamides, sulfonimidamides, sulfoximines, and sulfimides, which have recently attracted attention as pharmaceuticals and pesticides. − Sulfinamides can also be regarded as N -sulfinyl-protected amines, which are easily converted into the corresponding amines under acidic conditions . These valuable sulfur compounds are usually synthesized by the nucleophilic substitution of sulfinyl chlorides or sulfinate esters with amines or lithium amides (Scheme a). ,− However, the instability of highly reactive sulfinyl chlorides and lithium amides warrants the development of alternative, efficient methods.…”