Olefin with phosphoramidates

The conversion of ArN2 salts into ArH takes place in hexamethyl-phosphoramide (by a long radical chain process), and also by the use of the naphthalene anion radical CioHs" in THF. Alternatively, deamination of ArNH2 can be carried out with Bu ONO in DMF. Unsymmetrical biaryls can be formed in a phase-transfer reaction between the diazonium fluoroborate (in an arene solvent) and KOAc complexed with 18-crown-6 polyether. ° Meerwein aryl-ation of fluorinated olefins with ArN2 and copper(ii) halides has been described, but an alternative procedure for the overall addition of ArHal to an alkene involves the use of ArNH2, Bu ONO, and copper(ii) halides in acetone or... 

Chloro- and A TV-dichloro-phosphoramidate esters (20) and (21) are readily prepared from the parent phosphoramidate by direct chlorination in mildly acidic solution but when R = Ph, the use of t-butyl hypochlorite is preferable, to avoid chlorination of the aromatic nucleus. These compounds behave as pseudohalogens, (21) reacting with olefinic compounds such as styrene to give (22), which is also formed by chlorination of the N-phosphorylaziridine (23). ... 

This approach utilizes the platinum-catalyzed hydrosilylation reaction and requires both a,o)-hydrogen functional PDMS oligomers and free radical initiators bearing two olefinic double bonds. A series of such initiator compounds can be prepared in good to. excellent yields (40-80%) by the condensation of aryl ketones with vinyl substituted chlorosilanes in the presence of magnesium and a promoter such as N,N,N, N -tetramethylurea or hexamethyl-phosphoramide. 

Oxysulfenylation and oxyselenenylation of olefins, catalysed by chiral Brpnsted acids, have been reported to produce enantiomerically enriched tetrahydrofurans at <63% ee with dibenzoyl-tartaric acid and its derivatives as catalyst. Enantioselective desymmetrization of thiiranium and seleniranium ions (<50% and <84% ee, respectively) in the presence of chiral binaphthol-derived A(-triflyl phosphoramide as a catalyst has also been demonstrated. ... 

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