Base-Catalyzed Hydroamination of Olefins: An Environmentally Friendly Route to Amines

Abstract

The base‐catalyzed hydroamination of olefins offers a simple and elegant access to various primary, secondary, and tertiary amines. Particular focus is placed on developments in the area of hydroamination of non‐activated olefins. Advantages and disadvantages of the methodology compared to other synthetic methods are presented. Special attention is paid to potential industrial applications of this chemistry.

Fluorocarbon compatibilized gold-silica nanocomposites for recyclable regioselective hydroamination of alkynes in a fluorous biphasic system

“…Within the scope of the reactions, we also observed a zero conversion, for a substrate such as dec-1-yne with aniline. As minimum requirements, catalytic efficiencies measurable by turnover numbers (TONs: mole of product per mole of metal catalyst) of more than 1000 and by turnover frequencies (TOFs: the turnover per unit time) of more than 200 h -1 are generally considered [32]. Our catalytic material 4 satisfies the minimum TON requirement with measured TONs between 2300-4100.…”

Selective Catalytic Reductions of Amides and Nitriles to Amines

“…For recent reviews and highlights on iron catalysis see [66][67][68][69][70][71][72][73]. Also for some recent catalytic applications using iron catalysts from our group [74][75][76][77] 11 ], and Fe 2 (CO) 9 .…”

“…Applying 2 mol% of cheap Fe 3 (CO) 12 , an excellent yield (97%) of N,N-dimethylbenzylamine was obtained. Other iron sources, such as Fe 2 (CO) 9 , Fe(OAc) 2 , Fe(acac) 2 , and Fe(acac) 3 also showed conversion of the amide, but were less active. To our delight, he finally discovered that the reduction took place in the presence of inexpensive polymethylhydrosiloxane (PMHS) to give N,N-dimethylbenzylamine in 93% yield.…”

“…There is a continuing interest in the development of easier and cost-efficient methods for their synthesis (for some reviews see [2][3][4][5][6][7][8][9][10][11]). The reduction of amides is one of the most fundamental methods among the different procedures for preparing functionalized amines both on laboratory scale as well as in industry.…”

Asymmetric Hydroamination

“…While hydroamination catalysts based on transition metals have been studied intensively over the past two decades, only a limited number of reports on alkali metal-based hydroamination catalysts have emerged, although the first reports date back 60 years [71]. In particular, the application of chiral alkali metal complexes in asymmetric hydroamination of nonactivated aminoalkenes has drawn little attention to date [72,73].…”