Sulfinyl cyanides

Also notable are sulfur cyanide fluorides such as SF3CN,( 4°> SF2(CN)2 ° and SFjCN - ) and the sulfinyl cyanide fluoride FS(0)CN. " ° ... 

Sulfinyl cyanides N-Sulfinylimines Thiohydroxamic acids Thiohydroximic acids (esters)... 

Imino-l-sulfenic acids Oxathiol-2-ylidenimmonium salts Oxime sulfenates Sulfenyliminoesters Sulfinyl cyanides N-Sulfinylimines Thiohydroximic acids and esters... 

More recently, the addition of cyanide ion, generated from TMS cyanide and cesium fluoride, to a-aziridino N-siflfinyl imines, being chiral either at the a position or at sulfur, has been examined [87] (Scheme 28). The configuration of the newly formed stereocenter was determined only by the chiral (S)-sulfinyl group. In fact, the R configuration (diastereomeric excess, de, 98%) was obtained from either the Q -(ii)-imine 186 or the a-(S)-imine 188, giving 187 and 189, respectively. Acyclic 2,3-diaminonitriles can be obtained... 

A sulfinyl or sulfonyl group at the 2- or 4-position of a pyridine ring can be displaced by nucleophiles (i.e. alkoxides, thiolates, and cyanide) to afford the corresponding ipso substitution products. Similarly, 2-halo-6-methylsul-finyl- or 2-halo-6-methylsulfonylpyridines react with nucleophiles to give... 

Boger and Corbett have also recently described a convenient modification of the original Hudson methodology [20]. Their procedure is based upon the known [21] propensity of methanesulfonyl- and toluenesulfonyl cyanide to rearrange to the corresponding sulfinyl cyanate (cf. 8, Scheme 4). Thus, treatment of an oxime with commercially available tosyl cyanide (7) generates 8 in situ, which leads to the O-sulfinylated oxime 9 and then to the N-tosyl imine. This methodology avoids the use of reactive, often unstable sulfinyl chlorides. 

Strecker synthesis. N-Sulfimines add a cyanide ion from Et2AlCN preferentially from a coordination complex. Thus 1,3-asymmetric induction arises from the chiral sulfinyl unit. 

Carbenes are also intercepted by sulfoxides. For example, diazo compounds give sulfinyl ylides (155) during their decomposition by cuprous cyanide in the presence of a sulfoxide. 

Additional general methods for the synthesis of 7V-sulfonyl-imines based on the in situ generation of 0-sulfinate derivatives of oximes employing sulfinyl chlorides (phenyl- and methyl-sulfinyl chloride) or sulfonyl cyanides (p-toluenesulfonyl cyanide) and their subsequent rt rearrangement have been detailed. 

---