Herein, we report the regio‐ and chemoselective reactions of indole with carbamoyl electrophiles in presence of AlMe3. Indole‐3‐carboxamide was prepared in one‐step from a reaction of indole with tertiary carbamoylimidazole in the presence AlMe3. Under conditions for the formation of an aluminium ate complex, the reaction was diverted to the indole nitrogen. Secondary carbamoyl electrophiles in the presence of AlMe3 regiospecifically yielded trisubstituted ureas. The regiospecificity and chemoselectivity of the indole nitrogen towards ester and tertiary carbamoylimidazole functionalities were also studied.

An efficient and general method for the synthesis of unsymmetrical tetrasubstituted ureas from carbamoylimidazole is described. The conversion is achieved by the concurrent quarternization of the imidazole nitrogen and activation of amines with AlMe(3).

A simple, convenient and general method, exhibiting good functional group tolerance, is described for the synthesis of N‐ and N,N‐disubstituted amidines by the reaction of primary carboxamides with amines mediated by trimethylaluminium (AlMe3). Subsequent reaction of the indole systems with primary carboxamides in the presence of AlMe3 gives exclusively the C‐3 substituted imine product.

A general method for the synthesis of amidines is developed using the AlMe 3-promoted direct coupling of carboxylic amides with primary and secondary amines. Indoles undergo an analogous reaction to yield indole-3-acylimines. -(VELAVAN, A.; SUMATHI*, S.; BALASUBRAMANIAN, K. K.; Eur. J. Org. Chem. 2014, 26, 5806-5815, http://dx.doi.org/10.1002 Dep. Chem., Hindustan Univ., Chennai 603 103, India; Eng.) -Mais

A general and efficient access towards unsymmetrical urea derivatives is presented, involving the amination of carbamoylimidazoles in the presence of AlMe3.