Hydroaminomethylation amines effects

Under hydroformylation conditions, amines effect hydroaminomethylation to alkenes in an anti-Markovnikov sense. ... 

Hydroaminomethylation of alkenes occurred to give both n- and /. so aliphatic amines catalyzed by [Rh(cod)Cl]2 and [Ir(cod)Cl]2 with TPPTS in aqueous NH3 with CO/H2 in an autoclave. The ratio of n-and /.soprimary amines ranged from 96 4 to 84 16.178 The catalytic hydroaminomethylation of long-chain alkenes with dimethylamine can be catalyzed by a water-soluble rhodium-phosphine complex, RhCl(CO) (Tppts)2 [TPPTS P(m-C6H4S03Na)3], in an aqueous-organic two-phase system in the presence of the cationic surfactant cetyltrimethy-lammonium bromide (CTAB) (Eq. 3.43). The addition of the cationic surfactant CTAB accelerated the reaction due to the micelle effect.179... 

The hydroaminomethylation of 1-pentene and ammonia, with a Rh/Ir/TPPTS catalyst in an aqueous/organic two-phase system, was developed by BeUer et al. [14]. Under standard hydroformylation conditions (130°C, 12 MPa) amines could be isolated in 75% yield. By increasing the ammonia/olefin ratio and by using the extraction effect of the organic solvent as in Ref. [10], the selectivity for primary amines could reach more than 90%. This method could also be used for propene and 1-butene to give butylamine and pentylamine as main products. 

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