103437-97-4

Upstream product

• 99-94-5 p-Toluic acid 
• 110-83-8 cyclohexene 
• 22313-60-6 tert-butyl 4-methylbenzoperoxoate 
• 874-60-2 4-methyl-benzoyl chloride 
• 106-42-3 para-xylene 
• 110-82-7 cyclohexane 
• 142-71-2 copper diacetate 

Downstream Products

• 103438-01-3 c-2,t-3-dibromo-r-1-cyclohexyl p-methylbenzoate 
• 103530-06-9 t-2,c-3-dibromo-r-1-cyclohexyl p-methylbenzoate 
• 108345-19-3 4-Methyl-benzoic acid (1R,2S,6R)-2,6-dibromo-cyclohexyl ester 
• 108393-09-5 4-Methyl-benzoic acid (1S,2R,3S)-2,3-dibromo-cyclohexyl ester 

Relevant academic research and scientific papers

Copper porphyrin-catalyzed cross dehydrogenative coupling of alkanes with carboxylic acids: Esterification and decarboxylation dual pathway

A dual-functional copper porphyrin-catalyzed cross dehydrogenative coupling (CDC) of carboxylic acids with alkanes was reported firstly. The reaction gives allylic esters or alkylalkenes depending on the carboxylic acid substrates. Copper porphyrin catalyzed CDC method has the superiority of short reaction time, good functional group tolerance, base and solvent free, producing target products in an atom-economic manner.

Copper-iron mixed oxide supported onto cordierite honeycomb as a heterogeneous catalyst in the Kharasch-Sosnovsky oxidation of cyclohexene

A copper-iron mixed oxide was deposited by the washcoating procedure over cordierite honeycomb monoliths for its use as a heterogeneous catalyst in organic synthesis processes. In particular, the prepared catalyst, characterized by techniques such as X-ra

2-Aminopyrazine-functionalized MCM-41 nanoporous silica as a new efficient heterogeneous ligand for Cu-catalyzed allylic C–H bonds oxidation of olefins

In spite of the importance of the application of allylic C–H bond oxidation of olefins in organic synthesis and existence of the numerous reports, lots of limitations such as large excess of the olefin respect to the oxidant, low chemical yield, long time of reaction and a large amount of the catalyst were reminded. We introduced a novel catalytic system using functionalized MCM-41 as catalyst support to promote efficiency of this reaction. The heterogeneous ligand Pyr-MCM-41 was prepared by substituted 2-aminopyrazine ligand on functionalized MCM-41 with 3-chloropropyltrimthoxysilane and characterized by FT-IR, XRD, SEM, EDX, BET, TGA, CHN techniques. In situ immobilized Pyr-MCM-41 by copper (I) trifluoromethanesulfonate (CuOTf) was applied in direct catalytic esterification of inert C–H bonds in olefins using various peresters at room temperature.

Copper-catalyzed oxidative dehydrogenative functionalization of alkanes to allylic esters

Herein, we report a general, efficient and solvent-free method for the one-pot synthesis of allylic esters via dehydrogenation of unactivated alkanes and subsequent oxidative cross coupling with different substituted carboxylic acids. A simple, well defined and air stable Cu(II)-complex, [Cu(MeTAA)], featuring a tetraaza-macrocyclic ligand (tetramethyltetraaza[14]annulene (MeTAA)) is used as the catalyst. A wide variety of substituted allylic esters were synthesized in high yields starting from readily available starting materials. Control reactions were carried out to understand the reaction sequence and the plausible mechanism.

Copper porphyrin as efficient catalysts for esterification of allyl sp3 C–H bond with carboxylic acid

We described that copper 5,10,15,20-tetrakis (ethoxycarbonyl)porphyrin (TECP) catalyzed oxidative cross dehydrogenative coupling of allyl sp3 C–H bond with acid for the synthesis of allyl esters in a homogeneous system. This reaction proceeded

NHPI- and TBAI-Co-Catalyzed Synthesis of Allylic Esters from Toluene Derivatives and Alkenes

An N -hydroxyphthalimide (NHPI) and tetrabutylammonium iodide (TBAI) co-catalyzed oxidative coupling reaction of toluene derivatives and alkenes has been disclosed. This method can serve as a new strategy to access allylic ester using toluene derivatives as oxyacylating reagent. This metal-free protocol also features the readily available starting materials, broad substrate scope, and mild reaction conditions.

Iron-catalyzed esterification of allylic sp3 C–H bonds with carboxylic acids: Facile access to allylic esters

The first general and efficient iron-catalyzed esterification of allylic sp3 C–H bonds with carboxylic acids using ionic iron(III) complexes (1–4) as a catalyst and DTBP (DTBP?=?di-tert-butyl peroxide) as an oxidant is achieved. A variety of allylic esters were synthesized in good to excellent yields using the ionic iron(III) complex 2 as a catalyst in a 5?mol% loading. This reaction is characterized by its high efficiency, broad substrate scope with excellent steric hindrance tolerance and good functional group compatibility.

Copper-catalyzed oxidative coupling of acids with alkanes involving dehydrogenation: Facile access to allylic esters and alkylalkenes

We here describe a new copper-catalyzed oxidative coupling of acids with alkanes for the selective synthesis of allylic esters and alkylalkenes. This method achieves multiple dehydrogenation and esterification, representing a new unactivated C(sp3/s

Copper-catalyzed oxidative dehydrogenative carboxylation of unactivated alkanes to allylic esters via alkenes

We report copper-catalyzed oxidative dehydrogenative carboxylation (ODC) of unactivated alkanes with various substituted benzoic acids to produce the corresponding allylic esters. Spectroscopic studies (EPR, UV-vis) revealed that the resting state of the catalyst is [(BPI)Cu(O2CPh)] (1-O2CPh), formed from [(BPI)Cu(PPh3)2], oxidant, and benzoic acid. Catalytic and stoichiometric reactions of 1-O2CPh with alkyl radicals and radical probes imply that C-H bond cleavage occurs by a tert-butoxy radical. In addition, the deuterium kinetic isotope effect from reactions of cyclohexane and d12-cyclohexane in separate vessels showed that the turnover-limiting step for the ODC of cyclohexane is C-H bond cleavage. To understand the origin of the difference in products formed from copper-catalyzed amidation and copper-catalyzed ODC, reactions of an alkyl radical with a series of copper-carboxylate, copper-amidate, and copper-imidate complexes were performed. The results of competition experiments revealed that the relative rate of reaction of alkyl radicals with the copper complexes follows the trend Cu(II)-amidate > Cu(II)-imidate > Cu(II)-benzoate. Consistent with this trend, Cu(II)-amidates and Cu(II)-benzoates containing more electron-rich aryl groups on the benzamidate and benzoate react faster with the alkyl radical than do those with more electron-poor aryl groups on these ligands to produce the corresponding products. These data on the ODC of cyclohexane led to preliminary investigation of copper-catalyzed oxidative dehydrogenative amination of cyclohexane to generate a mixture of N-alkyl and N-allylic products.

Copper-catalyzed esterification of alkylbenzenes with cyclic ethers and cycloalkanes via C(sp3)-H activation following cross-dehydrogenative coupling

A copper-catalyzed cross-dehydrogenative coupling strategy has been developed for the synthesis of two classes of esters from simple solvents. The reaction of methylarenes with cyclic ethers resulted in α-acyloxy ethers involving four sp3 C-H cleavages, while treatment of methylarenes with cycloalkanes led to the formation of allyl esters at the expense of six consecutive sp3 C-H bonds.