86822-81-3

Upstream product

• 583-60-8 2-Methylcyclohexanone 
• 62-53-3 aniline 
• 108-86-1 bromobenzene 
• 151626-26-5 hept-6-en-1-amine 
• 4117-09-3 7-bromo-hept-1-ene 
• 39074-69-6 N-(6-hepten-1-yl)aniline 
• 13280-22-3 N-(2-methylcyclohexylidene)aniline 

Relevant academic research and scientific papers

An Aminopyridinato Titanium Catalyst for the Intramolecular Hydroaminoalkylation of Secondary Aminoalkenes

The easily accessible 2-(methylamino)pyridinato titanium complex initially synthesized by Kempe is used as catalyst for efficient intramolecular hydroaminoalkylation reactions of secondary aminoalkenes. The corresponding reactions of N-aryl-substituted 1-aminohept-6-enes and 1-aminohex-5-enes directly give access to 2-methylcyclohexyl- or 2-methylcyclopentylamines in good yields. In addition, intramolecular hydroaminoalkylations of an N-alkyl-substituted secondary aminoalkene and a geminally β-disubstituted substrate are described for the first time. While all products are formed as mixtures of two diastereoisomers, better trans/cis ratios are observed during the formation of 2-methylcylopentylamines.

Zinc-promoted, iridium catalyzed reductive alkylation of primary amines with aliphatic ketones in aqueous medium

The reductive alkylation of primary aromatic and aliphatic amines with aliphatic ketones has been achieved in aqueous acidic medium using commercially available, non-activated zinc dust catalyzed by a very small quantity of iridium bromide. Anilines react well in aqueous formic acid, whereas monoalkylamines require 1,4-dioxane as a co-solvent and sulfuric acid as the proton source. A plausible mechanism via low-valent iridium hydride species is proposed.

Direct, catalytic hydroaminoalkylation of unactivated olefins with N-alkyl arylamines

A tantalum-catalyzed addition of N-alkyl arylamine ∞-C-H bonds across olefins is reported. These reactions occur with mono- and 2,2-disubstituted olefins to form the branched insertion products in high yield and regioselectivity. The reactions encompass additions of the ∞-C-H bonds of cyclic and acyclic amines, as well as intramolecular additions. NMR studies indicate that the starting homoleptic, Ta(NMe2)5 precatalyst converts to bis- and tris(N-methylanilide) complexes (among others) in solution. Deuterium-labeling studies suggest that reversible ortho-metalation of the arene substituent occurs under the reaction conditions. However, several experiments imply that this ortho-metalation does not lie on the reaction pathway. Instead, these complexes are proposed to eliminate amine to form N-aryl imine complexes, which insert olefins into the Ta-C bond and undergo protonolysis to regenerate the active catalyst and eliminate the addition product. Copyright

Chemoselective reductive amination of aldehydes and ketones by dibutylchlorotin hydride-HMPA complex

Reductive amination of various aldehydes and ketones has been performed effectively by pentacoordinate chloro-substituted tin hydride complex, Bu2SnClH-HMPA. The tin reagent worked particularly well for the case using weakly basic aromatic amines as starting substrates. Stoichiometric amounts of a substrate and a reducing agent were adequate for the reaction. The Sn-Cl bond in the complex plays an important role for both steps of imine formation and subsequent reduction. Highly chemoselective reduction of carbonyls could be achieved regardless of other functionalities such as halogen, carbon- carbon double bond and hydroxyl groups in the starting carbonyls and amines.

Reductive Aminations of Ketones and Aldehydes using Borane-Pyridine

Borane-pyridine is introduced as a cheap and readily available alternative to sodium cyanotrihydroborate for the purpose of the reductive amination of a wide variety of carbonyl compounds.It does not suffer from the severe toxicity associated with sodium cyanotrihydroborate.

Stereoselective Reductions of Substituted Cyclohexyl and Cyclopentyl Carbon-Nitrogen ? Systems with Hydride Reagents

Reductions of 3- and 4-substituted cyclohexyl imines, iminium salts, and enamines (via iminium ions) with various hydride reagents reveal that while small reagents (NaBH4, NaBH3CN) favor axial approach as observed with the corresponding ketones, even moderately bulky reagents (i.e., acetoxyboranes) attack preferentially from the equatorial side.This is in direct contrast to the results observed for the same reagents with the corresponding ketones and is interpreted as implying that additional steric interactions induced by the nitrogen substituents encumber axial attack by substituted hydride reagents and force approach from the equatorial direction.The very bulky tri-sec-butylborohydride anion affords highly stereodiscriminating equatorial attack.Reductions of 2-alkylcyclohexyl and 2-alkylcyclopentyl imines and enamines also proceed with high stereoselectivity to give cis-2-alkyl cyclic amines with both hindered and unhindered reagents.This is interpreted to be the result of (1) augmented steric interactions between nitrogen substituents and equatorial 2-alkyl groups (1,3-allylic strain) which induces conformational changes to favor the axial 2-alkyl conformer and (2) hindrance toward equatorial approach by reagents induced by axial alkyl substituents.The result is that equatorial approach is favored with equatorial 2-alkyl conformers and preferential axial approach with axial 2-alkyl conformers, leading to stereoselective production of cis-2-alkylamines. trans-2-n-Propyl-4-tert-butylcyclohexanone is reduced by LiBH(sec-Bu)3 preferentially from the axial direction in contrast to the usual highly selective equatorial attack observed with other cyclohexanones.