New methods for the preparation of vicinal diamines and monoamines from olefins and cyanamide



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Two new vicinal diamination procedures have been developed beginning with unactivated alkenes 49 and cyanamide (50). These methods are marked by their simplicity and cost-efficiency. Moreover, these techniques proceeded Stereospecifically and permitted access to nitrogen unsubstituted diamines. Most alkenes 49 utilized in this study yielded the key bromocyanamide intermediates 52 upon treatment with cyanamide (50) and N-bromo- Succinimide (51). Bromocyanamides 52 were then converted to the vicinal diamines 1 in one of two ways. In a Solvolytic approach, condensation of cyanamides 52 with ethanol in the presence of anhydrous hydrochloric acid gave the corresponding protonated isourea salts 53. Treatment 53 with mild bases (triethyl amine, sodium bicarbonate) in select cases yielded imidazolines 57. Alternatively, use of strongly basic conditions (sodium ethoxide or sodium hydroxide) led to the predominant formation of aziridines 55. These aziridines could be converted to imidazolines 57 with various nucleophilic catalysts. The scope of this isomerization was examined. Basic hydrolysis of the imidazolines 57 in the final step yielded the desired vicinal diamines 1 in 47-71% overall yield. [...]



Organic compounds--Synthesis, Polyamines, Amines