84487-66-1

Upstream product

• 100-17-4 para-methoxynitrobenzene 
• 110-83-8 cyclohexene 
• 104-94-9 4-methoxy-aniline 
• 1165952-91-9 cyclohexa-1,3-diene 
• 822-67-3 Cyclohex-2-enol 
• 2101-87-3 p-methoxy-phenylazide 
• 1521-51-3 rac-3-bromocyclohexene 
• 33948-36-6 2-iodocyclohex-2-en-1-one 
• 1384752-98-0 (±)-7-(4-methoxyphenyl)-7-azabicyclo[4.1.0]heptan-2-one 

Downstream Products

• 1373492-49-9 diethyldithiocarbamic acid [(4-methoxyphenyl)(cyclohex-2-enyl)carbamic acid]thioanhydride 
• 1373492-56-8 (±)-(1R,6S)-7-(4-methoxyphenyl)-7-azabicyclo[4.2.0]oct-2-en-8-one 

Relevant academic research and scientific papers

A lutidine-promoted photoredox catalytic atom-transfer radical cyclization reaction for the synthesis of 4-bromo-3,3-dialkyl-octahydro-indol-2-ones

Reported herein is a visible-light-catalyzed photoredox atom-transfer radical cyclization (ATRC) halo-alkylation of 1,6-dienes with α-halo-ketones as the ATRC reagent. This process exhibits high atom economy, high step economy, and high redox economy, which can directly construct a 4-bromo-3,3-dialkyl-octahydro-indol-2-one core under mild conditions in one pot, and lutidine is found to be the key promoter for this ATRC process.

Hydrogen-Borrowing Amination of Secondary Alcohols Promoted by a (Cyclopentadienone)iron Complex

Thanks to a highly active catalyst, the scope of the (cyclopentadienone)iron complex-promoted 'hydrogen-borrowing' (HB) amination has been expanded to secondary alcohols, which had previously been reported to react only in the presence of large amounts of co-catalysts. A range of cyclic and acyclic secondary alcohols were reacted with aromatic and aliphatic amines giving fair to excellent yields of the substitution products. The catalyst was also able to promote the cyclization of diols bearing a secondary alcohol group with primary amines to generate saturated N-heterocycles.

Synthesis and catalytic activity of μ-oxo ruthenium(IV) porphyrin species to promote amination reactions

This work describes the synthesis of ruthenium(IV) m-oxo porphyrin complexes of general formula [RuIV(TPP)(X)]2O which have been applied as catalysts in nitrene transfer reactions using aryl azides (ArN3) as nitrene sources. Collected data indicated that the catalytic efficiency of [RuIV(TPP)(OCH3)]2O was comparable to that of RuII(TPP)CO because of their analogous reactivity towards aryl azides to give the same catalytically active bis-imido species RuVI(TPP)(ArN)2. The reaction of [RuIV(TPP)(OCH3)]2O with Ph3CN3 or (CH3)3SiN3 afforded [RuIV(TPP)(N3)]2O which was fully characterised, its molecular structure was also determined by single crystal X-ray analysis.

Copper-Catalyzed Intramolecular Oxidative Amination of Unactivated Internal Alkenes

A copper-catalyzed oxidative amination of unactivated internal alkenes has been developed. The Wacker-type oxidative alkene amination reaction is traditionally catalyzed by a palladium through a mechanism involving aminopalladation and β-hydride elimination. Replacing the precious and scarce palladium with a cheap and abundant copper for this transformation has been challenging because of the difficulty associated with the aminocupration of internal alkenes. The combination of a simple copper salt, without additional ligand, as the catalyst and Dess-Martin periodinane as the oxidant, promotes efficiently the oxidative amination of allylic carbamates and ureas bearing di- and trisubstituted alkenes leading to oxazolidinones and imidazolidinones. Preliminary mechanistic studies suggested a hybrid radical-organometallic mechanism involving an amidyl radical cyclization to form the key C-N bond.

The aza-wharton reaction: Syntheses of cyclic allylic amines and vicinal hydroxyamines from the respective acylaziridines

The Wharton reaction, initially described for acyl epoxides, has been studied using the structurally similar aziridines. By this reaction, a range of cyclic allylic amines and vicinal amino alcohols have been prepared stereoselectively and, in some cases, enantiomerically pure.

Synthesis of 1-arylcycloalkenamines by intramolecular arylation of lithiated ureas

The deprotonation of N′-arylurea derivatives of cyclohexenamines by alkyllithiums leads to migration of the N′-aryl substituent from N′ to the allylic position α to N via rearrangement of a urea-stabilised allyllithium intermediate. The product ureas may be solvolysed to reveal 1-arylcyclohexenamines.

Insights into the mechanism of the ruthenium-porphyrin-catalysed allylic amination of olefins by aryl azides

This paper describes the synthesis of allylic amines by aryl azides (ArN3) catalysed by [Ru(TPP)CO] (TPP = dianion of tetraphenylporphyrin). The employment of aryl azides renders the methodology sustainable as the formation of molecular nitrogen is the only stoichiometric byproduct. The isolation of catalytic intermediates and spectroscopic and kinetic studies revealed interesting information about the reaction mechanism, which could improve its catalytic efficiency in future research. An important result is the X-ray characterisation of [Ru(TPP)(ArN)2] [Ar = 3,5-(CF3)2C6H3], which is active in both stoichiometric and catalytic nitrene transfer reactions. The proposed involvement of carbonyl-monoimido-ruthenium porphyrin complexes in the catalytic cycle is also derived from our kinetic and experimental results. All the data indicate the coexistence of two mechanisms, where the electronic nature of the engaged aryl azide and olefin concentration determine one mechanism or the other. Copyright

Semipinacol rearrangement of cis-fused β-lactam diols into keto-bridged bicyclic lactams

The 6-azabicyclo[3.2.1]octane ring system, prevalent in a range of biologically active molecules, is prepared through a novel semipinacol rearrangement utilizing a cyclic phosphorane or sulfite intermediate. The rearrangement proceeds with exclusive N-acyl group migration of a β-lactam ring and results in carbonyl functionality at the 7- and bridging 8-position of the bicycle. Precursor ring-fused β-lactam diols are prepared through a sequence of 4-exo trig carbamoyl radical cyclization, regioselective dithiocarbamate group elimination, and dihydroxylation.

Nucleophilic substitution reactions of alcohols with use of montmorillonite catalysts as solid Bronsted acids

(Chemical Equation Presented) We have developed an environmentally benign synthetic approach to nucleophilic substitution reactions of alcohols that minimizes or eliminates the formation of byproducts, resulting in a highly atom-efficient chemical process. Proton- and metal-exchanged montmorillonites (H- and Mn+-mont) were prepared easily by treating Na +-mont with an aqueous solution of hydrogen chloride or metal salt, respectively. The H-mont possessed outstanding catalytic activity for nucleophilic substitution reactions of a variety of alcohols with anilines, because the unique acidity of the H-mont catalyst effectively prevents the neutralization by the basic anilines. In addition, amides, indoles, 1,3-dicarbonyl compounds, and allylsilane act as nucleophiles for the H-mont-catalyzed substitutions of alcohols, which allowed efficient formation of various C-N and C-C bonds. The solid H-mont was reusable without any appreciable loss in its catalytic activity and selectivity. Especially, an Al3+-mont showed high catalytic activity for the α-benzylation of 1,3-dicarbonyl compounds with primary alcohols due to cooperative catalysis between a protonic acid site and a Lewis acidic Al3+ species in its interlayer spaces.

Hydroamination of 1,3-cyclohexadiene with aryl amines catalyzed with acidic form zeolites

The intermolecular hydroamination of 1,3-cyclohexadiene with aniline using zeolite catalysts was investigated. The reaction mechanism and the influence of amine basicity on the rate of reaction were studied. Zeolite H-BEA was the most active catalyst, whereas the incorporation of Zn2+ (Zn/H-BEA) led to decreasing catalytic activity, indicating that the reaction is catalyzed by Bronsted acid sites. Subtle shape selective effects determine the reactivity and selectivity of the zeolites.