N-Alkylation of Amines with Alcohols Catalyzed by Manganese(II) Chloride or Bromopentacarbonylmanganese(I)

Abstract

A manganese-catalyzed N-alkylation reaction of amines with alcohols via hydrogen autotransfer strategy has been demonstrated. The developed practical catalytic system including an inexpensive, nontoxic, commercially available MnCl2 or MnBr­(CO)5 as the metal salt and triphenylphosphine as a ligand provides access to diverse aromatic, heteroaromatic, and aliphatic secondary amines in moderate-to-high yields. In addition, this operationally simple protocol is scalable to the gram level and suitable for synthesizing heterocycles such as indole and resveratrol-derived amines known to be active for Alzheimer’s disease.

Four- and five-coordinate nickel(ii) complexes bearing new diphosphine–phosphonite and triphosphine–phosphite ligands: catalysts for N-alkylation of amines

“… 21 We are interested in homogeneous catalysis using well-defined, new molecular metal complexes. Among metal complexes containing Ru, 22 Rh, 23 Ir, 24 Au, 25 Mn, 26 Co, 27 Fe, 28 Pd 29 metals, nickel complexes catalyzed reactions remains attractive because of the above mentioned reasons in addition to their salts being cheaper. Hence, several efficient nickel complexes have been reported to catalyze N -alkylation reactions.…”

Highly Efficient and Recyclable Porous Organic Polymer Supported Iridium Catalysts for Dehydrogenation and Borrowing Hydrogen Reactions in Water

“…It was very pleasing to find that N‐benzyl‐aniline ( 4 a ) was obtained in good yield. Compared to traditional catalysts, such as manganese chloride, [12a] copper(I) chloride, [12b] copper acetate and zinc acetate, even, IrCl 3 , Pd(OAc) 2 , RuCl 3 , etc ., POP‐MBTS‐Ir catalyst could be reused at least five times and the desired 4 a was achieved with good yields in water. (More detailed data of optimization of reaction conditions, please see Table S2 in SI.).…”

Manganese-catalyzed hydrogenation, dehydrogenation, and hydroelementation reactions

“…Most recently, the group of Peng reported an N -alkylation reaction in the presence of MnCl 2 or MnBr(CO) 5 /PPh 3 catalytic system ( Mn99 ) and a stoichiometric amount of KO t Bu (Table 21, entry 11). 326 This protocol was successfully applied to the alkylation of a wide range of aniline derivatives. However, benzyl amines, secondary amines, and aliphatic amines failed to give the desired product.…”