Direct Amination of Bio‐Alcohols Using Ammonia

Abstract

A slightly adapted catalyst system has been successfully applied in the direct amination of primary and secondary alcohols. Moreover, the applicability to diols has been shown, giving high selectivity towards the primary diamines. It was found that the Ru/P ratio as well as the amount of ammonia used are highly important in this system, especially for higher substrate loadings. The catalyst was employed on a larger batch scale for the conversion of isomannide to the corresponding diamine. Additionally, it was shown that the catalyst is stable for at least six consecutive runs. No significant loss of activity and selectivity was observed.

Diamines for Polymer Materials via Direct Amination of Lipid‐ and Lignocellulose‐based Alcohols with NH3

“…[40] Moreover,t his system seems to be most promising as this and derivatives of this, have been employed successfully in the direct amination of variousd iols, including ab ranched dimer fatty acid (C 36 )d iol. [44] Another system based on RuHCl(-CO)(PPh 3 ) 3 and Xantphos as ligand,d eveloped by the Beller group, wasr eportedt ob ee ffective for diols and long-chain (mono)alcohols. [44] Another system based on RuHCl(-CO)(PPh 3 ) 3 and Xantphos as ligand,d eveloped by the Beller group, wasr eportedt ob ee ffective for diols and long-chain (mono)alcohols.…”

“…[46,51] System C2 is also based on the acridine-based diphosphine ligand, but with ruthenium carbonyl as metal source,p roviding as omewhat more robusts ystem. [44] Another system based on RuHCl(-CO)(PPh 3 ) 3 and Xantphos as ligand,d eveloped by the Beller group, wasr eportedt ob ee ffective for diols and long-chain (mono)alcohols. [43] The most recent catalyst( C4)i sb ased on RuHCl(CO)(PPh 3 ) 3 and the Triphos ligand, [45] which is also knownt obe ag ood hydrogenation catalyst.…”

“…[1,35] Also in case of 5-HMF derived amines, no direct catalytic, atom-efficient routes are currently availablea nd still rely on multi-step routes producing significant amounts of waste. [40][41][42][43][44][45] However,o nly two exampleso fal ong-chain diol direct amination have been reported, both for the case of 1,19-nonadecane diol, and the conversion of the product to polymers as ap robe of their suitability to this purposehas been lacking. [40][41][42] To date, severals ystems have been developed that efficientlyc onvert primary and secondary alcohols to primary amines.…”

“…[40][41][42] To date, severals ystems have been developed that efficientlyc onvert primary and secondary alcohols to primary amines. [40][41][42][43][44][45] However,o nly two exampleso fal ong-chain diol direct amination have been reported, both for the case of 1,19-nonadecane diol, and the conversion of the product to polymers as ap robe of their suitability to this purposehas been lacking. [46,47,51] This is, however,crucial as it is also as ensitive probe whether the amination reactioni s sufficiently selective and the formation of problematic (e.g.…”

Reductive Amination of 2-Amino-2-methyl-1-propanol and Ammonia to Produce 2-Methyl-1,2-propanediamine over Raney Nickel Catalyst

“…However, yields and selectivities are rather low in the synthesis of aliphatic diamines from the corresponding diols and ammonia. As for the homogeneous catalysts, ruthenium‐catalyzed amination of diols with aqueous ammonia was reported for the synthesis of diamine, but selective synthesis of primary amines remains as a challenging task ,. Recently, the first example of the selective synthesis of diamine from 1,10‐decanediol and ammonia using biocatalytic methods was reported .…”