PdCl 2 in the presence of dppe or Xantphos(t-Bu) as the ligand is found to be an efficient catalyst for the N-alkylation of various primary and cyclic secondary amines using primary alcohols at 90−130 °C under neat conditions. Interestingly, good to excellent yields were achieved when more challenging secondary alcohols were used as alkylating agents at 130−150 °C. The reaction could be easily scaled up, as demonstrated for a 10 mmol scale achieving yields up to 90% with a TON of 900.

Simple non-chelating ruthenium benzimidazolin-2-ylidene complexes as efficient N-alkylation catalysts using alcohols and diols following a hydrogen borrowing strategy.

A silica supported palladium-NiXantphos complex is reported as an efficient and a high turnover heterogeneous catalyst for the N-alkylation of amines and the a-alkylation of ketones using readily available alcohols under neat conditions at 120-140 C following hydrogen borrowing strategy. The catalyst is easily separable and offers negligible amount of palladium leaching (<0.01 ppm). A high turnover number of about 46 000 for the N-alkylation of amines and 4400 for the a-alkylation of ketones were achieved in the respective single batch reactions. The catalyst is recyclable up to four times without appreciable change in catalytic performance.

Efficient and recyclable ruthenium catalysts were synthesized from readily available polystyrene‐ or silica‐supported phosphine ligands. Catalysts bound to the polymer support through an ether linkage showed good to excellent activity towards the N‐alkylation of primary and secondary amines to afford the alkylated products in 62–99 % yield at 120–140 °C. The supported phosphine ligand/ruthenium ratio was found to be crucial for higher catalytic activity and lower ruthenium leaching. The continuous flow N‐alkylation of amines was demonstrated by using the supported catalyst in a column reactor. By adopting the hydrogen‐borrowing strategy, the synthesis of the anti‐Parkinson agent Piribedil was established in 98 % yield at 140 °C.