Efficient New Protocols for Converting Primary Amides into Nitriles Initiated by P(NMe2)3, PCl3, or P(OPh)3.

Three efficient and high-yielding procedures have been developed for the conversion of primary amides into nitriles, mediated by hitherto unexplored P(NMe2)3, PCl3, or P(OPh)3. The reactions were conducted under operationally simple and mild conditions and displayed broad substrate scope and good functional group tolerance.

Application of Ynamides in the Synthesis of 2-(Tosylamido)- and 2,5-Bis(tosylamido)thiophenes.

A step-economic and metal-catalyst-free synthesis of 2-(tosylamido)- and 2,5-bis(tosylamido)-thiophenes from nonsymmetrical 1,3-butadiynamides and symmetrical 1,3-butadiyne-1,4-diamides is reported. The reaction proceeds in the presence of Na2S·9H2O (2-3 equiv) under mild reaction conditions (50 °C) and is facilitated by polarized carbon-carbon triple bonds in ynamides. This new approach to thiophenes based on the chemistry of ynamides was applied to the synthesis of a bis(tosylamido)-capped terthiophene having a string of N,S-heteroatoms embedded in a highly π-conjugated molecular frame.