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

Xiao-yan, Chen; Yang, Shuang; Ren, Bao-Ping; Shi, Lei; Lin, Dong-Zi; Zhang, Hao; Liu, Haiyang

doi:10.1016/j.tet.2021.132377

Cited by 6 publications

(4 citation statements)

References 48 publications

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“…33 What's more, 1ac could not be formed only in presence of a catalyst or oxidizer (Scheme 3, viii). Based on the above results as well as the reported literatures, 32,34 we can infer the CDC reaction catalyzed by CuTPP where the benzaldehyde firstly underwent oxidation followed by the formation of cyclohexene, and cyclohexene was produced before C(sp 3 )-O bond formation. In addition, the kinetic isotope effect (KIE) was investigated by intermolecular competing experiments (Scheme 4).…”

Section: Accepted Manuscriptsupporting

confidence: 78%

Copper Porphyrin Catalyzed C(sp3)–H Activation via Cross-Dehydrogenative Coupling: Facile Transformation of Aldehydes to Esters

Shan¹,

Chen²,

Zhang³

et al. 2022

Synlett

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Copper porphyrin-catalyzed alkane C−H bond functionalization with aldehydes via cross dehydrogenative coupling (CDC) using DTBP oxidant has been firstly described in non-solvents or non-additives system. Different aryl/heteroaryl-carboxilic esters were obtained in good to excellent yields depending on the aldehyde derivatives. This CDC reaction catalyzed by copper porphyrin has the advantages of shorter reaction time, lower reaction temperature and catalyst loading as well as the aerobic reaction atmosphere.

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Section: Accepted Manuscriptsupporting

confidence: 78%

Copper Porphyrin Catalyzed C(sp3)–H Activation via Cross-Dehydrogenative Coupling: Facile Transformation of Aldehydes to Esters

Shan¹,

Chen²,

Zhang³

et al. 2022

Synlett

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“…The direct C–H functionalization of nonactivated alkanes is still relatively scarce due to their intrinsic low reactivity. Acyloxylation of C(sp 3 )–H bonds in alkanes was achieved with [Au]/PIDA, Co(OAc) 2 /I 2 /NHPI/O 2 /HNO 3 , H 2 O 2 /TFA, Selectfluor/CuBr 2 /pentanenitrile, TFAN/TFA, RuCl 3 /AcOOH/TFA, Fe(III)/O 2 /TFA/ hv , and [Mn]/H 2 O 2 . , In some cases, it was difficult to avoid overoxidation of the product, which led to allyl esters (CuTPP/DTBP, Cu(OAc) 2 / TBHP, [(BPI)CuCl]/ DTBP, and CuO/DTBP).…”

Section: Resultsmentioning

confidence: 99%

Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp³)–H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides

et al. 2023

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The reaction of Ni(II) acetate with diacyl peroxides produces high-valence Ni-species capable of catalytic oxidative acyloxylation of C(sp3)–H bonds in ethers, ketones, and alkanes. The desired esters were obtained in 20–82% yields. Computational analysis suggests that activation of the peroxide moiety produces a dynamically interconverting mixture of catalytic Ni-species in the formal Ni(III) state. Remarkably, in these species, coordination of the RCO2 group at Ni preserves radical character at the carboxylate moiety (i.e., carboxylate radical acts as an “L-ligand”), so the latter can induce fast C–H abstraction. The spirocyclopropyl moiety prevents premature radical decarboxylation via a combination of hybridization factors and stereoelectronic effects. A variety of viable C–H activation patterns were identified experimentally and computationally.

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“…Among these catalysts, metal porphyrin has attracted extensive attentions for its good catalytic activity in the oxidation reaction of the wide scope of ketone substrates. [15] In 2008, metal porphyrin was firstly used as aerobic B-V oxidation catalyst. The best yield of ɛcaprolactone is 96% by using 20 mol% iron porphyrin Fe-(TPP)Cl.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Metal Xanthene‐Bridged Bis‐corroles and their Catalytic Activity in Aerobic Baeyer‐Villiger Oxidation Reaction

Tang

Huang

et al. 2022

Asian J Org Chem

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The metal (M=Co, Cu, Mn, Sn, Fe) xanthene-bridged bis-corroles (M 2 XBC) were synthesized and used for catalyzing aerobic Baeyer-Villiger (B-V) oxidation of cyclic ketones to corresponding lactones. It turns out iron (IV) bis-corrole complex (Fe 2 XBC) exhibited excellent activity and selectivity towards the B-V oxidation of various cyclic ketones at very low catalyst loading. The yield of ɛ-caprolactone could reach 98% with only 0.005 mol% catalyst. The turnover number (TON) of the Fe 2 XBC catalyst could even be up to 17400 in a gram-scale oxidation of cyclohexanone, showing the promising for industrial usage. Moreover, the existences of benzoyl radical and benzoylperoxy radical in the reaction were proved by ESI-HRMS spectra and electron paramagnetic resonance (EPR) spectra. A plausible radical mechanism for the metal bis-corrole catalyzed aerobic B-V oxidation of cyclohexanone in the presence benzaldehyde additive was proposed.

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

Cited by 6 publications

References 48 publications

Copper Porphyrin Catalyzed C(sp3)–H Activation via Cross-Dehydrogenative Coupling: Facile Transformation of Aldehydes to Esters

Copper Porphyrin Catalyzed C(sp3)–H Activation via Cross-Dehydrogenative Coupling: Facile Transformation of Aldehydes to Esters

Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp³)–H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides

Synthesis of Metal Xanthene‐Bridged Bis‐corroles and their Catalytic Activity in Aerobic Baeyer‐Villiger Oxidation Reaction

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

Cited by 6 publications

References 48 publications

Copper Porphyrin Catalyzed C(sp3)–H Activation via Cross-Dehydrogenative Coupling: Facile Transformation of Aldehydes to Esters

Copper Porphyrin Catalyzed C(sp3)–H Activation via Cross-Dehydrogenative Coupling: Facile Transformation of Aldehydes to Esters

Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp3)–H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides

Synthesis of Metal Xanthene‐Bridged Bis‐corroles and their Catalytic Activity in Aerobic Baeyer‐Villiger Oxidation Reaction

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Creating, Preserving, and Directing Carboxylate Radicals in Ni-Catalyzed C(sp³)–H Acyloxylation of Ethers, Ketones, and Alkanes with Diacyl Peroxides