The alkylation of amines by alcohols has been achieved using 0.5 mol % [Ru(p-cymene)Cl(2)](2) with the bidentate phosphines dppf or DPEphos as the catalyst. Primary amines have been converted into secondary amines, and secondary amines into tertiary amines, including the syntheses of Piribedil, Tripelennamine, and Chlorpheniramine. N-Heterocyclization reactions of primary amines are reported, as well as alkylation reactions of primary sulfonamides. Secondary alcohols require more forcing conditions than primary alcohols but are still effective alkylating agents in the presence of this catalyst.

The use of [Cp*IrI 2 ] 2 as an efficient catalyst for the alkylation of amines by alcohols in either water or ionic liquid is described. Primary amines are converted into secondary amines, and secondary amines into tertiary amines in the absence of base, and the chemistry has been applied to the synthesis of the analgesic fentanyl. The conversion of primary amines into N-heterocycles by the reaction with diols is also described, along with the N-alkylation of sulfonamides.

Amination O 0268Ruthenium-Catalyzed N-Alkylation of Amines and Sulfonamides Using Borrowing Hydrogen Methodology. -A ruthenium catalyst with a bidentate phosphine ligand successfully catalyzes the conversion of primary amines into secondary amines, and secondary amines into tertiary amines including the synthesis of a few pharmaceuticals such as Piribedil (VIf). Additionally, N-heterocyclization reactions of primary amines (XIV) and the alkylation of sulfonamides are reported. The reaction is most readily accomplished using unbranched primary alcohols with sterically unencumbered amines, although other substrates could also be used. -(HAMID, M. H. S. A.; ALLEN, C. L.; LAMB, G. W.; MAXWELL, A. C.; MAYTUM, H. C.; WATSON, A. J. A.; WILLIAMS, J. M. J.; J.