Sulfinamides, reaction with

Of great importance was the discovery by Johnson et al. (185) of the stereospecific synthesis of optically active sulfonimidoyl chlorides, which are key substrates for making new types of sulfonimidoyl compounds. The method involves chlorination of readily available chiral sulfinamides with chlorine or A/-chlorobenzotriazole. Scheme 12 summarizes the synthesis of (-)-(/ )-A/-methylphenylsulfonimidoyl chloride 163 from (+HS>N-methyl benzenesulfinamide 164 and its reactions with sodium phenoxide and dimethylamine. 

Ab initio calculations have been earned out on the gas-phase acid-catalysed hydrolysis reactions of sulfinamide (319) using the 3-21G sets.290 The first step in the acid-catalysed hydrolysis of A-methylmethanesulfinamide (319 R1 = R2 = Me) is O-protonation and this form is then transformed by addition of water to the sulfiirane intermediate (320). Intramolecular proton transfer from 0 to N follows and then slow N—S bond cleavage to give products.290 Studies with (319 R1 = Me, R2 =aryl) also... 

Violent reaction with alcohols, N-aryl sulfinamides, dimethyl formamide, polychlorobiphenyl, sodium hydroxide, hydrochloric acid + dinitroanilines. Incandescent reaction when warmed with cesium oxide (above 150°), tellurium, arsenic, tungsten dioxide. Potentially dangerous reaction with hydrocarbons + Lewis acids releases toxic and reactive HCl gas. 

In their 1975 paper on ene reactions with ditosyl sulfodiimide 78, Kresze et al. briefly mentioned that N-sulfinyl sulfonamide 100 undergoes ene reactions with alkenes to yield S-2-alkenyl sulfinamides 101 (Scheme 27) [63]. Contrasting the behavior of the aza analogues, the S-allylsulfamidines (Type E, Sect. 3.1), the resulting 2-alkenyl sulfinamides 101 are not prone to sigma-tropic rearrangement. This, on the other hand, can be taken as a hint that... 

An asymmetric variant of this kind of allylic amination, based on their phenylcyclohexanol-derived chiral N-sulfinyl carbamates, was developed by Whitesell et al. (see also Sect. 3.2) (Scheme 34) [85]. After the asymmetric ene reaction with Z-configured olefins (not shown) had occurred, nearly di-astereomerically pure sulfinamides 127 were obtained which were found to be prone to epimerization. Their rapid conversion via O silylation and [2,3]-a rearrangement dehvered the carbamoylated allyhc amines 128 with around 7 1 diastereoselectivity as crystalline compounds that can be recrystallized to enhance their isomeric purity to 95 5. Obviously the imiform absolute configuration at Cl in the ene products 127 was difficult to transfer completely due to the already mentioned ease of epimerization. Unhke the sulfonamides of Delerit (Scheme 33) [84], the carbonyl moiety can easily be cleaved by base treatment. 

The administration of TNT to laboratory animals leads to the excretion of 4-NHOH-DNT, 2-NH2-DNT, and 4-NH2-DNT in the urine [59], and to the formation of covalent adducts with microsomal liver and kidney proteins, hemoglobin, and other blood proteins [60], The acid hydrolysis of adducts yielded mainly 2-NH2-DNT (2-ADNT) and 4-NH2-DNT (4-ADNT). Incubation of rat liver microsomes with TNT and NADPH under aerobic conditions resulted in the formation of NH2-DNTs and the transient metabolite 4-NHOH-DNT [57], The formation of covalent protein adducts with TNT metabolites was enhanced by the presence of 02 and decreased by GSH. This is consistent with the scheme of the TNT adduct formation with the central role of the nitroso metabolite (NO-DNT) reaction with protein or nonprotein thiols (RSH Equation 9.11) [57], The acid hydrolysis of the sulfinamide adduct (RS(0)-NH-DNT) formed after the rearrangement of the semimercaptal (RS-N(OH)-DNT Equation 9.12) will yield NH2-DNT. The mixture of NHOH-DNTs inhibits bacterial glyceraldehyde-3-phosphate dehydrogenase and glucose-6-phosphate dehydrogenase more efficiently than TNT [61]. This was attributed to the covalent modification of protein -SH groups. 

Eq. 9). Recently, these reactions were repeated with sulfinamide anhydride ... 

Wudl and Lee [27] developed this idea based on marked difficulty in cleaving the S—bond of acyclic sulfinamides compared to the S—O bond of sulfinates [28]. (17 ,25)-(-)-Ephedrine was employed to obtain a diastereoisomeric mixture of cyclic 1,2,3-oxathiazolidine 2-oxides (21) and (22) on reaction with thionyl chloride (Scheme 2.19). 

Sulfinate and Phosphate Esters. Anhydrides of sulhnic and sulfonic acids and phosphate monoesters can be prepared using DCC. Further reaction with alcohols or phenols gives the corresponding sulfinates and phosphate diesters. Pyrophosphates can be prepared from mono- and disubstituted phosphate esters. Reaction of activated sulfinates with amines gives the corresponding sulfinamides. ... 

Double asymmetric induction operates when the azomethine compound is derived from a chiral a-amino aldehyde and a chiral amine, e.g., the sulfin-imine 144 [70]. In this case, the R configuration at the sulfur of the chiral auxihary, N-tert-butanesulfinamide, matched with the S configuration of the starting a-amino aldehyde, allowing complete stereocontrol to be achieved in the preparation of the diamine derivatives 145 by the addition of trifluo-romethyl anion, which was formed from trifluoromethyltrimethylsilane in the presence of tetramethylammonium fluoride (Scheme 23). The substituents at both nitrogen atoms were easily removed by routine procedures see, for example, the preparation of the free diamine 146. On the other hand, a lower diastereoselectivity (dr 80 20) was observed in one reaction carried out on the imine derived from (it)-aldehyde and (it)-sulfinamide. 

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