- Copper porphyrin-catalyzed cross dehydrogenative coupling of alkanes with carboxylic acids: Esterification and decarboxylation dual pathway
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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.
- Chen, Xiao-Yan,Yang, Shuang,Ren, Bao-Ping,Shi, Lei,Lin, Dong-Zi,Zhang, Hao,Liu, Hai-Yang
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- Copper-iron mixed oxide supported onto cordierite honeycomb as a heterogeneous catalyst in the Kharasch-Sosnovsky oxidation of cyclohexene
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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
- Fellak, M. Amine,Gatica, José M.,Guerra, Francisco M.,Moreno-Dorado, F. Javier,Vidal, Hilario,Yeste, M. Pilar
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- Copper-catalyzed oxidative dehydrogenative functionalization of alkanes to allylic esters
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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.
- Mondal, Rakesh,Chakraborty, Gargi,van Vliet, Kaj M.,van Leest, Nicolaas P.,de Bruin, Bas,Paul, Nanda D.
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supporting information
(2019/11/11)
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- Copper porphyrin as efficient catalysts for esterification of allyl sp3 C–H bond with carboxylic acid
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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
- Xiong, Ming-Feng,Ali, Atif,Akram, Waseem,Zhang, Hao,Si, Li-Ping,Liu, Hai-Yang
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- NHPI- and TBAI-Co-Catalyzed Synthesis of Allylic Esters from Toluene Derivatives and Alkenes
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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.
- Li, Chengliang,Deng, Hongmei,Jin, Tao,Li, Chunju,Jia, Xueshun,Li, Jian
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supporting information
p. 840 - 844
(2018/01/27)
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- Copper porphyrin catalyzed esterification of C(sp3)-H via a cross-dehydrogenative coupling reaction
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The crystal structure of 5,10,15,20-tetra(ethoxycarbonyl)porphyrin copper(ii) showed that its central copper has a six-coordinate structure. An efficient copper porphyrin-catalyzed cross-dehydrogenative coupling (CDC) esterification reaction between C(sp
- Wang, Hua-Hua,Wen, Wei-Hong,Zou, Huai-Bo,Cheng, Fan,Ali, Atif,Shi, Lei,Liu, Hai-Yang,Chang, Chi-Kwong
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supporting information
p. 3508 - 3514
(2017/07/12)
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- Iron-catalyzed esterification of allylic sp3 C–H bonds with carboxylic acids: Facile access to allylic esters
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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.
- Lu, Bing,Zhu, Fan,Wang, Dan,Sun, Hongmei,Shen, Qi
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supporting information
p. 2490 - 2494
(2017/05/31)
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- Cobalt-catalyzed oxidative esterification of allylic/benzylic C(sp3)–H bonds
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A protocol for the cobalt-catalyzed oxidative esterification of allylic/benzylic C(sp3)–H bonds with carboxylic acids was developed in this work. Mechanistic studies revealed that C(sp3)–H bond activation in the hydrocarbon was the turnover-limiting step and the in-situ formed [Co(III)]Ot-Bu did not engage in hydrogen atom abstraction (HAA) of a C–H bond. This protocol was successfully incorporated into a synthetic pathway to β-damascenone that avoided the use of NBS.
- Ren, Tian-Lu,Xu, Bao-Hua,Mahmood, Sajid,Sun, Ming-Xue,Zhang, Suo-Jiang
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supporting information
p. 2943 - 2948
(2017/04/26)
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- Copper-catalyzed oxidative coupling of acids with alkanes involving dehydrogenation: Facile access to allylic esters and alkylalkenes
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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
- Wang, Cheng-Yong,Song, Ren-Jie,Wei, Wen-Ting,Fan, Jian-Hong,Li, Jin-Heng
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supporting information
p. 2361 - 2363
(2015/02/05)
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- Copper-catalyzed oxidative dehydrogenative carboxylation of unactivated alkanes to allylic esters via alkenes
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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.
- Tran, Ba L.,Driess, Matthias,Hartwig, John F.
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supporting information
p. 17292 - 17301
(2015/02/02)
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- Cu(II)/TBAI-catalyzed esterification of acid hydrazides via C(sp3)-H oxidative coupling
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A Cu2+/TBAI-cocatalyzed allylic ester synthesis was developed, which allows a direct coupling of acid hydrazides and cycloalkanes. This process makes use of commercially available, inexpensive, and abundant starting materials. Based on the extensive experimental data, a plausible radical mechanism was suggested.
- Liu, Guifeng,Jin, Can,Wu, Guomin
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supporting information
p. 2908 - 2912
(2015/01/16)
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- Copper-catalyzed esterification of alkylbenzenes with cyclic ethers and cycloalkanes via C(sp3)-H activation following cross-dehydrogenative coupling
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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.
- Rout, Saroj Kumar,Guin, Srimanta,Ali, Wajid,Gogoi, Anupal,Patel, Bhisma K.
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supporting information
p. 3086 - 3089
(2014/06/23)
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- Cu-catalyzed C(sp3)-H bond activation reaction for direct preparation of cycloallyl esters from cycloalkanes and aromatic aldehydes
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Cu-catalyzed dehydrogenation-olefination and esterification of C(sp 3)-H bonds of cycloalkanes with TBHP as an oxidant has been developed. The reaction involves four C-H bond activations and gives cycloallyl ester products directly from cycloalkanes and aromatic aldehydes.
- Zhao, Jincan,Fang, Hong,Han, Jianlin,Pan, Yi
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supporting information
p. 2530 - 2533
(2014/05/20)
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- Allylic oxidation of alkenes catalyzed by a copper-aluminum mixed oxide
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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.
- Garcia-Cabeza, Ana Leticia,Marin-Barrios, Ruben,Moreno-Dorado, F. Javier,Ortega, Maria J.,Massanet, Guillermo M.,Guerra, Francisco M.
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supporting information
p. 1598 - 1601
(2014/04/17)
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- Tetrabutylammonium iodide catalyzed synthesis of allylic ester with tert -butyl hydroperoxide as an oxidant
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A metal-free C-H oxidation for the construction of allylic esters has been developed. The use of a commercially available and inexpensive catalyst and oxidant, and readily available starting materials, coupled with the operational simplicity of the reacti
- Shi, Erbo,Shao, Ying,Chen, Shulin,Hu, Huayou,Liu, Zhaojun,Zhang, Jie,Wan, Xiaobing
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supporting information; experimental part
p. 3384 - 3387
(2012/08/08)
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- Allylic Carboxylations and Lactonization Using Benzoquinone and Hydrogen Peroxide or tert-Butyl Hydroperoxide as Oxidants
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Two new systems have been developed for catalytic carboxylation of alkenes.Both use palladium(II) as catalyst and benzoquinone as cocatalyst.In the first hydrogen peroxide was used as oxidant in acetic acid solution.Alkenes such as cyclohexene and 5-decene were converted cleanly to allylic acetates, but with 1-decene mainly the methyl ketone was formed.A diene such as 1,3-cyclohexadiene gave the diacetate while cis-1,2-divinylcyclohexane gave the cyclized monoacetate.In the second system, tert-butyl hydroperoxide was used as oxidant, permitting a wider choice of solvents and nucleophiles.Intramolecular reaction to lactones was possible in addition to allylic addition of acids such as benzoic, pivalic, and (S)-O-acetylmandelic acid.
- Akermark, Bjoern,Larsson, E. Magnus,Oslob, Johan D.
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p. 5729 - 5733
(2007/10/02)
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