- Convenient C(sp3)-H bond functionalisation of light alkanes and other compounds by iron photocatalysis
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Light alkanes are natural organic carbon sources and widely distributed in nature. Transforming them into value-added fine chemicals affords attractively economic and ecological benefits as well as enormous chemical challenges. Herein, we report a practical iron-catalysed photoredox system for C(sp3)-H transformation of ethane, propane, and other light alkanes to C-N and C-C bonds under ambient temperature. The present method with abundant and inexpensive iron salts as photocatalysts exhibits high catalytic efficiency (turnover number up to 8000), mild conditions, and the convenience of being purified and scaled up without chromatography. A photo-induced ligand-to-metal charge transfer between Fe(iii) and Cl- generates a highly active chlorine radical that sequentially acts as hydrogen atom transfer catalyst. Therefore, the sustainable, convenient, and environmentally friendly system will find wide applications in high-value-added transformation of natural alkanes with novel inspiration not only for organic synthesis, but also for designing catalytically active organic/inorganic materials. This journal is
- Duan, Chunying,Jin, Yunhe,Meng, Changgong,Wang, Lifang,Wang, Xinyao,Zhang, Qingqing
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supporting information
p. 6984 - 6989
(2021/09/28)
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- Rhodium-Catalyzed Carbonylative Coupling of Alkyl Halides with Phenols under Low CO Pressure
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A rhodium-catalyzed carbonylative transformation of alkyl halides under low pressure of CO has been developed. This robust catalyst system allows using phenols as the carbonylative coupling partner and, meanwhile, exhibits high functional group tolerance and good chemoselectivity. Substrates even with a large steric hindrance group or multiple reaction sites can be selectively converted into the desired products in good to excellent yields. A gram-scale experiment was performed and delivered an almost quantitative amount of the product. Control experiments were performed as well, and a possible reaction mechanism is proposed.
- Ai, Han-Jun,Li, Chong-Liang,Wang, Hai,Wu, Xiao-Feng
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p. 5147 - 5152
(2020/05/27)
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- Visible-light-initiated manganese-catalyzed Giese addition of unactivated alkyl iodides to electron-poor olefins
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Herein, we report a mild protocol for direct visible-light-initiated Giese addition of unactivated alkyl iodides to electron-poor olefins (Michael acceptors) with catalysis by decacarbonyl dimanganese, Mn2(CO)10, an inexpensive earth-abundant-metal catalyst. This protocol is compatible with a wide array of sensitive functional groups and has a broad substrate scope with regard to both the alkyl iodide and the Michael acceptor.
- Dong, Jianyang,Wang, Xiaochen,Wang, Zhen,Song, Hongjian,Liu, Yuxiu,Wang, Qingmin
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supporting information
p. 11707 - 11710
(2019/10/02)
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- Catalyst-free Decarboxylation and Decarboxylative Giese Additions of Alkyl Carboxylates through Photoactivation of Electron Donor-Acceptor Complex
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We report herein a catalyst-free method to perform decarboxylative conjugated addition and hydrodecarboxylation of aliphatic N-(acyloxy)phthalimides (redox active esters, RAEs) through photoactivation of electron-donor-acceptor (EDA) complex with Hantzsch ester (HE) in N,N-dimethylacetamide (DMA) solution. The reactions present a green method to decarboxylatively construct carbon-carbon bond and to perform hydrodecarboxylation with broad substrate scope and functional group tolerance under mild blue light irradiation condition without recourse of popularly used photoredox catalysts. (Figure presented.).
- Zheng, Chao,Wang, Guang-Zu,Shang, Rui
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supporting information
p. 4500 - 4505
(2019/08/26)
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- Catalyst-free alkyl carboxylate decarboxylation and decarboxylation Giese radical addition reaction
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A catalyst-free alkyl carboxylate decarboxylation and decarboxylation Giese radical addition reaction is as follows: in a solution environment, an alkyl N-(acyloxy) phthalimide compound, hantzsch ester and an alkenyl compound react in an inert protective atmosphere under blue violet light irradiation with a wavelength range of 370-470 nm, and the equivalent ratio of alkyl N-(acyloxy) phthalimide compound to hantzsch ester to alkenyl compound is 1: 1-3: 1-2. The photoactivated hantzsch ester is converted into free radicals. Under the attack of the free radicals, the alkyl N-(acyloxy) phthalimide compound can undergo decarboxylation reaction without a catalyst and Giese radical addition reaction with the alkenyl compound.
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Paragraph 0068-0102
(2019/11/20)
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- Decarboxylation and decarboxylation Giese free radical addition reactions of alkyl carboxylate of photo-activated electron donor-acceptor complex
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The invention discloses decarboxylation and decarboxylation Giese free radical addition reactions of alkyl carboxylate of a photo-activated electron donor-acceptor complex. In a solution environment,a compound represented in the description, Hantzsch ester and Rb carry out reactions in an inert protective atmosphere under the irradiation of blue-purple light with a wavelength of 370-470 nm, wherein the equivalent ratio of the compound to Hantzsch ester to Rb is 1:1-3:1-2. After photo activation, Hantzsch ester is converted into a free radical; under the attack of the free radical, decarboxylation happens in the absence of a catalyst, and the free radical and a compound with an alkenyl group carry out Giese free radical addition reactions.
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Paragraph 0054; 0061-0066; 0068-0069; 0081-0086; 0089-0090
(2019/11/28)
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- Pd-Catalyzed Regiodivergent Hydroesterification of Aryl Olefins with Phenyl Formate
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An effective Pd-catalyzed regiodivergent hydroesterification of aryl olefins with phenyl formate is described. Either linear or branched phenyl arylpropanoates can be obtained in good yields with high regioselectivities by the judicious choice of ligand without the use of toxic CO gas.
- Ren, Wenlong,Chang, Wenju,Wang, Yang,Li, Jingfu,Shi, Yian
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supporting information
p. 3544 - 3547
(2015/07/28)
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- Thermal Addition of Alkanes to Alkenes, II. Addition of Cyclohexane to Acrylate in a Free Radical Chain Reaction
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Alkanes can be added to alkenes in a thermally initiated reaction.Kinetic studies on the addition of cyclohexane to phenyl acrylate clearly revealed that a radical chain reaction is involved.The results can only be satisfactorily explained in terms of a symproportionation of the alkane and the alkene to give two alkyl radicals.This initiation reaction is very slow (220C: ki 610-13lmol-1s-1, t1/2 3104a).Kinetic isotopic effects of the initiation reaction and of the H-transfer reaction from cyclohexane to alkyl radical 6b have been measured. β-Scission of the intermediate adduct radicals has been measured as well.Quite normal reaction rates are observed near the critical point of cyclohexane.
- Hartmanns, Joerg,Klenke, Kurt,Metzger, Juergen O.
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p. 488 - 499
(2007/10/02)
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