Selective Amine Cross‐Coupling Using Iridium‐Catalyzed “Borrowing Hydrogen” Methodology

Abstract

Ganz ohne Basen kann der Iridiumkomplex [{Cp*IrI2}2] (Cp*=C5Me5) Kreuzkupplungen von Aminen katalysieren. Eine Reihe von Anilinen wurde in die entsprechenden N‐Isopropyl‐Derivate überführt; die gleiche Reaktion ermöglichte auch die Alkylierung von Benzylaminen und anderen aliphatischen primären Aminen.

Synthesis of Primary Amines from Secondary and Tertiary Amines: Ruthenium‐Catalyzed Amination Using Ammonia

“…In this respect, the conversion of secondary amines into primary ones is an attractive transformation. Although Williams and co-workers [13] and our group [14] have shown that secondary and even tertiary amines can be activated and used in the alkylation of aliphatic and aromatic amines, to the best of our knowledge no similar reactions with ammonia have been reported, yet.…”

Rh‐Catalyzed Reductive Cyclization of Enynes Using Ethanol as a Source of Hydrogen

“…Recently, the CÀC bond formation by borrowing hydrogen (dehydrogenative alcohol activation) has been developed. [11] As far as we are aware, this is the first practical use of hydrogen generated from ethanol in the reductive cyclization of enynes. An enantioselective reductive cyclization in the presence of hydrogen gas and rhodium catalyst had been reported [9b] several years ago and ethanol has been used in diene hydro-hydroxyethylation.…”

Ruthenium‐Catalyzed Nitro and Nitrile Compounds Coupling with Alcohols: Alternative Route for N‐Substituted Amine Synthesis

“…Firstly, the reductive alkylation of 4-nitrotoluene with various benzylic alcohols containing methyl, methoxyl, and chloro groups were performed. Clearly, all these reactions progressed well and 83-95 % isolated yields were achieved (entries [1][2][3][4][5]. Then, the alteration of nitrobenzenes was performed.…”

“…[1] N-Substituted amines are usually prepared by the alkylation of amines with halides. [2] However, this method is problematic due to overalkyation, the toxic nature of halides and related alkylating reagents, and the generation of stoichiometric unwanted byproducts. In many cases, N-substituted amines could also be synthesized by hydroamination [3] and hydroaminomethylation [4] reactions.…”