32720-57-3

Upstream product

• 110-91-8 morpholine 
• 5401-62-7 1,2-dibromocyclohexane 
• 1165952-91-9 cyclohexa-1,3-diene 
• 52034-22-7 3-anilinocyclohexene 
• 110-83-8 cyclohexene 
• 822-67-3 Cyclohex-2-enol 
• 76644-52-5 rac-3-acetoxycyclohexene 

Downstream Products

• 92-53-5 4-Phenylmorpholine 
• 19307-62-1 2-(1-methyl-2-nitroethyl)cyclohexanone 

Relevant academic research and scientific papers

C-N Bond Formation from Allylic Alcohols via Cooperative Nickel and Titanium Catalysis

Amination of allylic alcohols is facilitated via cooperative catalysis. Catalytic Ti(O-i-Pr)4 is shown to dramatically increase the rate of nickel-catalyzed allylic amination, and mechanistic experiments confirm activation of the allylic alcohol by titanium. Aminations of primary and secondary allylic alcohols are demonstrated with a variety of amine nucleophiles. Diene-containing substrates also cyclize onto the nickel allyl intermediate prior to amination, generating carbocyclic amine products. This tandem process is only achieved under our cooperative catalytic system.

Micellar catalysis using a photochromic surfactant: Application to the pd-catalyzed tsuji-trost reaction in water

The first example of a Pd-catalyzed Tsuji-Trost reaction, applied in a photochromic micellar media under conventional heating and microwave irradiation, is reported. The surfactant activity and recycling ability were investigated and compared with those of a few commercially available surfactants. The synthetic photochromic surfactant proved to be efficient, recyclable, and versatile for Pdcatalyzed coupling reactions.

Transition Metal-Catalyzed C-H Amination Using Unactivated Amines

One aspect of the invention relates to a method of animation or amidation, comprising the step of combining a substrate, comprising a reactive C—H bond, and an amine or amide, comprising a reactive N—H bond, in the presence of an oxidizing agent and a metal-containing catalyst, thereby forming a product with a covalent bond between the carbon of the reactive C—H bond and the nitrogen of the reactive N—H bond.

Allylic amination via decarboxylative C-N bond formation

This manuscript details the development of a palladium-catalyzed allylic amination that proceeds via decarboxylation of allylic carbamates. Both saturated and aromatic heterocycles undergo decarboxylative rearrangement in good yields. The mechanism of allylation of heteroaromatic amines involves the formation of π-allyl palladium complexes followed by decarboxylation of the carbamate. Finally, the heteroaromatic anion equivalent is allylated to provide allylic amines. Georg Thieme Verlag Stuttgart.

A general nickel-catalyzed hydroamination of 1,3-dienes by alkylamines: Catalyst selection, scope, and mechanism

A simple colorimetric assay of various transition-metal catalysts showed that the combination of DPPF, Ni(COD)2, and acid is a highly active catalyst system for the hydroamination of dienes by alkylamines to form allylic amines. The scope of the reaction is broad; various primary and secondary alkylamines react with 1,3-dienes in the presence of these catalysts. Detailed mechanistic studies revealed the individual steps involved in the catalytic process. These studies uncovered unexpected thermodynamics for the addition of amines to π-allyl nickel complexes: instead of the thermodynamics favoring the reaction of a nickel allyl with an amine to form an allylic amine, the thermodynamics favored reaction of a nickel(0) complex with allylic amine in the presence of acid to form a Ni(II) allyl. The realization of these thermodynamics led us to the discovery that nickel and some palladium complexes in the presence or absence of acid catalyze the exchange of the amino groups of allylic amines with free amines. This exchange process was used to reveal the relative thermodynamic stabilities of various allylic amines. In addition, this exchange reaction leads to racemization of allylic amines. Therefore, the relative rate for C-N bond formation and cleavage influences the enantioselectivity of diene hydroaminations.

Transition metal-catalyzed process for addition of amines to carbon-carbon double bonds

The present invention is directed to a process for addition of amines to carbon-carbon double bonds in a substrate, comprising: reacting an amine with a compound containing at least one carbon-carbon double bond in the presence a transition metal catalyst under reaction conditions effective to form a product having a covalent bond between the amine and a carbon atom of the former carbon-carbon double bond. The transition metal catalyst comprises a Group 8 metal and a ligand containing one or more 2-electron donor atoms. The present invention is also directed to enantioselective reactions of amine compounds with compounds containing carbon-carbon double bonds, and a calorimetric assay to evaluate potential catalysts in these reactions.

Transition metal-catalyzed process for addition of amines to carbon-carbon double bonds

The present invention is directed to a process for addition of amines to carbon-carbon double bonds in a substrate, comprising: reacting an amine with a compound containing at least one carbon-carbon double bond in the presence a transition metal catalyst under reaction conditions effective to form a product having a covalent bond between the amine and a carbon atom of the former carbon-carbon double bond. The transition metal catalyst comprises a Group 8 metal and a ligand containing one or more 2-electron donor atoms. The present invention is also directed to enantioselective reactions of amine compounds with compounds containing carbon-carbon double bonds, and a calorimetric assay to evaluate potential catalysts in these reactions.

Nickel- and Palladium-Catalyzed Additions of Nucleophiles to Cyclic 1,3-Dienes

Carbon nucleophiles have been found to add smoothly to 1,3-cyclohexadiene using either a preformed nickel-ligand complex or Ni(0) prepared by in situ reduction of Ni(II) in the presence of a ligand to give 1,2- and 1,4-addition products.Analogous adducts were also obtained from 1,3-cyclopentadiene and 1,3-cyclooctadiene, but the yields were considerably lower.Attempts to add benzenesufinic acid to 1,3-cyclohexadiene using Ni(0) were unsuccessful; this reaction was instead found to be catalyzed by Pd(0)-phosphite complexes.