Oxyamination

V-(p-Toluenesulphonyl)sulphilimines have been prepared under solidtliquid phase-transfer catalytic conditions from the reaction of sulphides with Chloramine-T [25] (see Section 4.5). Osmium-catalysed oxyamination of alkenes by Chloramine-T under two-phase conditions is aided by the addition of benzyltriethylammonium chloride. p-Aminoalkanols are obtained in good yields (60-75%) [26]. 

The mono-unsaturated disaccharide 74 was also prepared (4 ). It was obtained in 93% yield by condensation of 6g with 2,3,4,6-tetra-0-benzyl -et-D-qlucose under catalysis ( 7) with stannic chloride.Preliminary experiments indicated that it can likewise be oxyaminated (48). If this is borne out in further studies, a route would be open to the D-manno,D-gluco stereoisomers of and 57. 

Another approach for the synthesis of networks relies on the polycondensation of multifunctionalized polyesters with the appropriate multifunctionalized agent, provided that one of the partner is at least tri-functionalized. Toward this end, several reaction have been reported, such as the Michael addition of amines onto acrylates [184], the coupling of ketones and oxyamines [185], the click copper(II)-catalyzed azide-alkyne cycloaddition [186], and esterification reactions [25, 159, 187]. Interestingly, if esterification reactions are used, the crosslinks are then degradable. 

I. Dyong and N. Jersch, Synthesis of important carbohydrates. 18. The v/c-ds-oxyamination as the key reaction for amino sugar syntheses Methyl A-acetyl-4-epi-a-garosaminide, Chem. Ber., 112 (1979) 1849-1858. 

Oxyamination.2 The reagent has been used to effect hydroxyamination of alkencs with aryl amines (equation I). The rearranged isomer 1 is the major product with terminal alkenes (R3 = R4 = H). 

OXYAMINATION Mercury(ll) oxide-Tetrafluoroboric acid. Trioxn(/-butyl-imido)osmium (VIII). 

Nitrogen-transfer reactions of osmium imido species lead to cis diamines or amino alcohols. Reaction of 0s02(N-/-C4H9)2 [63174-13-0] with olefins produces vicinal diamines after reductive cleavage. Catalytic oxyamination of olefins using chloramine-T or AJ-chlor-AJ-argenocarbamates yields vicinal hydroxy toluenesulfonamides (112) or carbamates (113), respectively, which maybe deprotected to vicinal amino alcohols. 

The same researchers found that imino derivatives of Os04 react with alkenes to produce cis-jS-amino alcohols (equation 124).346,347 This oxyamination reaction can be made catalytic in the presence of chloramine salts, e.g. ArS02NClNa or ROCONClAg.348,349... 

Methyl-l,3-diselenonylidene)piperidinium perchlorate, 3168 (9-Methyl-/V,/V-disilyl hydroxyl amine, 0513 Methylenebis(nitramine), 0481 Methylenebis(3-nitramino-4-methylfurazan), 2801 Methylenebis(oxyamine), 0502b... 

---