Tosylated amines, oxidative amination

Bis(3-methylsulfonyloxypropyl) amine HCI Improsulfan tosylate Bismuth oxide... 

Treatment of (5,5)-/>/.v(2-hydroxypropyl)phcnylphosphine oxide with initially base followed by Cl(CH2)20(CH2)20Tf gave the dichloride intermediate, which with base and either catechol or tosyl amine in DMF and elevated (150 °C) temperatures generated the macrocyclic phosphane oxide 35 in 15% yield or the l-phospha-10-aza-18-crown-6-ether in 44% yield <06EJOC154>. 

An electrochemical method for amination has been reported by Shono and co-workers.275 Derivatives of malonic esters containing an N-tosyl group were cyclized in high yields by anodic oxidation ... 

Tertiary amines are oxidized to the corresponding nitrogen oxides. Tosyl hydrazones of ketones and aldehydes and imines are oxidized to the corresponding carbonyl compounds. Reactions have been carried out with small molecules and also with molecules that would not diffuse into the pore structure of the titanium silicates. As in the case of C—C bond cleavage, it is possible that these reactions take place on the outer surface of the catalyst crystals. 

Predict the products of reactions of amines with ketones and aldehydes, alkyl halides and tosylates, acid chlorides, sulfonyl chlorides, nitrous acid, and oxidizing agents. Propose mechanisms where appropriate. 

Polymers with pendant carbodiimide groups 27 are also synthesized from crossUnked polystyrene. In this synthetic route crossUnked polystyrene beads are chloromethylated and converted to the amines. Reaction with isopropyl isocyanate gives the corresponding ureas, which are treated with tosyl chloride and triethylamine to produce the crossUnked polycarbodiimides. This polymer is used in the polymer supported Moffatt oxidation of alcohols into aldehydes or ketones using benzene/DMSO. ... 

Even poor nucleophiles such as the amides 46 can react with azines in the presence of alkynes as activating agents [59, 60]. Various nucleophiles (including alkoxides, thiols, amines and nitrogen heterocycles) were recently employed in a related process with Ai-oxide azaindoles (Reissert-Henze reaction. Scheme 10). In the process, the oxygen is alkylated with dimethyl sulfate and, after the nucleophilic attack, methanol is released to aromatize the initial adduct [61,62]. Following similar mechanistic trends, V-heteroatom-activated azines afford the corresponding substituted adducts. Likewise, W-tosylated isoquinoline [63, 64] and W-fluoropyridinium salts [65] are also reactive substrates in Reissert-Henze type processes. 

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