Ruthenium(II) Complexes with N-Heterocyclic Carbene-Phosphine Ligands for the N-Alkylation of Amines with Alcohols

Metal hydride complexes are key intermediates for N-alkylation of amines with alcohols by borrowing hydrogen/hydrogen autotransfer (BH/HA) strategy. Reactivity tuning of metal hydride complexes could adjust the dehydrogenation of alcohols...

Cross β-arylmethylation of alcohols catalysed by recyclable Ti–Pd alloys not requiring pre-activation

Recyclable and pre-activation free Ti–Pd alloy catalysts promote cross β-alkylation of primary alcohols via hydrogen autotransfer.

Tungsten-Catalyzed Direct N-Alkylation of Amines with Alcohols

The implementation of earth-abundant metals mediated chemistry is a major goal in homogeneous catalysis. Borrowing hydrogen/hydrogen autotransfer (BH/HA) reaction, as a straightforward and sustainable synthetic method, has attracted considerable attention in the development of earth-abuandant metal catalysts. Herein, we report a tungsten-catalyzed <i>N</i>-alkylation reaction of amines with primary alcohols via BH/HA. This phosphine-free W(phen)(CO)₄ (phen=1,10-phenthroline) system was demonstrated as a practical and easily accessible <i>in-situ</i> catalysis for a broad range of amines and alcohols (up to 49 examples, including 16 previously undisclosed products). Notably, this tungsten system can tolerate numerous functional groups, especially the challenging substrates with sterically hindered substituents, or heteroatoms. Mechanistic insights based on experimental and computational studies are also provided.

Tungsten-Catalyzed Direct N-Alkylation of Amines with Alcohols

The implementation of earth-abundant metals mediated chemistry is a major goal in homogeneous catalysis. Borrowing hydrogen/hydrogen autotransfer (BH/HA) reaction, as a straightforward and sustainable synthetic method, has attracted considerable attention in the development of earth-abuandant metal catalysts. Herein, we report a tungsten-catalyzed <i>N</i>-alkylation reaction of amines with primary alcohols via BH/HA. This phosphine-free W(phen)(CO)₄ (phen=1,10-phenthroline) system was demonstrated as a practical and easily accessible <i>in-situ</i> catalysis for a broad range of amines and alcohols (up to 49 examples, including 16 previously undisclosed products). Notably, this tungsten system can tolerate numerous functional groups, especially the challenging substrates with sterically hindered substituents, or heteroatoms. Mechanistic insights based on experimental and computational studies are also provided.