41321-26-0Relevant articles and documents
Copper-catalyzed oxidative dehydrogenative functionalization of alkanes to allylic esters
Mondal, Rakesh,Chakraborty, Gargi,van Vliet, Kaj M.,van Leest, Nicolaas P.,de Bruin, Bas,Paul, Nanda D.
supporting information, (2019/11/11)
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.
Iron-catalyzed esterification of allylic sp3 C–H bonds with carboxylic acids: Facile access to allylic esters
Lu, Bing,Zhu, Fan,Wang, Dan,Sun, Hongmei,Shen, Qi
supporting information, p. 2490 - 2494 (2017/05/31)
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 dehydrogenative carboxylation of unactivated alkanes to allylic esters via alkenes
Tran, Ba L.,Driess, Matthias,Hartwig, John F.
supporting information, p. 17292 - 17301 (2015/02/02)
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.
Metal-free, one-pot synthesis of allylic and benzylic esters via decarboxylation and C-H bond activation
Mo, Hanjie,Chen, Dingben,Xu, Lingzhen,Chen, Di,Pan, Fuyou,Yang, Jianguo
supporting information, p. 209 - 215 (2015/05/05)
A tetrabutylammonium iodide catalyzed method has been developed for the one-pot synthesis of allylic and benzylic esters from α-oxo carboxylic acids and alkenes/alkylbenzenes via decarboxylation and C-H bond activation. Various allylic and benzylic esters were obtained in good yield.
Allylic oxidation of alkenes catalyzed by a copper-aluminum mixed oxide
Garcia-Cabeza, Ana Leticia,Marin-Barrios, Ruben,Moreno-Dorado, F. Javier,Ortega, Maria J.,Massanet, Guillermo M.,Guerra, Francisco M.
supporting information, p. 1598 - 1601 (2014/04/17)
A strategy for the allylic oxidation of cyclic alkenes with a copper-aluminum mixed oxide as catalyst is presented. The reaction involves the treatment of an alkene with a carboxylic acid employing tert-butyl hydroperoxide as the oxidant. In all cases, the corresponding allylic esters are obtained. When l-proline is employed, the allylic alcohol or ketone is obtained. The oxidation of cyclohexene and valencene has been optimized by design of experiments (DoE) statistical methodology.
Hydroxyselanylation of acyloxycyclohex-3-enes
Sweeney,Haughan, Alan F.,Knight,Thobhani, Smita
, p. 2729 - 2737 (2007/10/03)
In contrast to the corresponding hydroxyiodination reactions, the reaction of acetoxycyclohex-2-ene 1 with N-PSP in the presence of water shows little regiocontrol, but is highly diastereoselective. However, the same reaction of the (R)-phenylglycinate de
