- Determination of the Minimum-Energy Conformation of Allylbenzene and Its Clusters with Methane, Ethane, Water, and Ammonia
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Supersonic molecular jet laser time-of-flight mass spectroscopy (TOFMS) is employed to determine the minimum energy conformation of the allyl group with respect to the benzene ring of allylbenzene, 1-allyl-2-methylbenzene, and 1-allyl-3-methylbenzene.The
- Breen, P. J.,Bernstein, E. R.,Seeman, Jeffrey I.,Secor, Henry V.
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Read Online
- Aryl C-F bond functionalization preparation method
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The invention relates to the technical field of organic compound synthesis, in particular to an aryl C-F bond functionalization preparation method. A fluorobenzene compound and a nucleophilic reagent react under the action of a composite catalyst, wherein the composite catalyst is formed by mixing a visible light catalyst and a metal catalyst. The photocatalyst is adopted, the reaction process is safe and controllable, and operation in the preparation and production process is simplified; a purple LED is used as a reaction energy source and is green and environment-friendly, the energy utilization rate is high, and conversion from light energy to chemical energy can be efficiently realized; in the reaction, a simple nucleophilic reagent is used for attacking free radical cation species generated under a visible light catalysis condition, so that a target product with an extremely wide range is efficiently and greenly prepared; the operation steps are simplified, and the reaction route is shortened; and moreover, the forward reaction rate is high, and the production efficiency is remarkably improved.
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Paragraph 0052; 0054-0061
(2021/09/29)
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- Palladium-Catalyzed meta-C-H Olefination of Arene-Tethered Diols Directed by Well-Designed Pyrimidine-Based Group
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The palladium-catalyzed meta-olefination of arene-tethered diols attached to a well-designed pyrimidine moiety is presented. Applications of the protocol are illustrated by the synthesis of various diol-based natural products, such as coumarins, phenylpropanoids, stilbenes, and chalcones. Advantages of this method are demonstrated through the easy removal of the template and a gram-scale olefination reaction. Finally, experimental verification, including 1H NMR, ESI-MS and IR, and DFT studies are undertaken to elucidate the mechanistic complexity.
- Fang, Siqiang,Wang, Xiaobing,Yin, Fucheng,Cai, Pei,Yang, Huali,Kong, Lingyi
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supporting information
(2019/03/19)
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- Catalytic Oxidative Trifluoromethoxylation of Allylic C?H Bonds Using a Palladium Catalyst
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A catalytic intermolecular allylic C?H trifluoromethoxylation reaction of alkenes has been developed based on the use of a palladium catalyst, CsOCF3 as the trifluoromethoxide source, and benzoquinone as the oxidant. This reaction provides an efficient route for directly accessing allylic trifluoromethoxy derivatives with excellent regioselectivities from terminal alkenes via an allylic C?H bond activation process.
- Qi, Xiaoxu,Chen, Pinhong,Liu, Guosheng
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supporting information
p. 9517 - 9521
(2017/08/01)
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- Palladium-catalyzed oxidative allylation of bis[(pinacolato)boryl]methane: Synthesis of homoallylic boronic esters
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A palladium-catalyzed oxidative allylation of bis[(pinacolato)boryl]methane to afford the corresponding homoallylic organoboronic esters with moderate to excellent yields is reported. This novel transformation provides an efficient strategy for the construction of homoallylic organoboronic esters in one step with a broad substrate scope. It is proposed that the palladium-catalyzed oxidative allylic C-H bond activation process may be involved in the catalytic cycle.
- Li, Chunsheng,Li, Meng,Li, Jianxiao,Wu, Wanqing,Jiang, Huanfeng
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supporting information
p. 66 - 69
(2017/12/27)
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- Palladium-catalyzed aerobic oxidative double allylic C-H oxygenation of alkenes: A novel and straightforward route to α,β-unsaturated esters
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A mild tandem oxidative functionalization of allyl aromatic hydrocarbons was accomplished using the catalytic system of Pd(OAc)2/DMA under 1 atm O2. The green twofold C-O bond formation involving double allylic C-H oxygenation unlocks opportunities for markedly different synthetic strategies. Moreover, the reaction affords aryl α,β-unsaturated esters directly from readily available terminal olefins in moderate to good yields with excellent chemo- and stereoselectivities.
- Yang, Wanfei,Chen, Huoji,Li, Jianxiao,Li, Chunsheng,Wu, Wanqing,Jiang, Huanfeng
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supporting information
p. 9575 - 9578
(2015/06/08)
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- Efficient double bond migration of allylbenzenes catalyzed by Pd(OAc) 2-HFIP system with unique substituent effect
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A novel catalyst system of Pd(OAc)2-HFIP induces double-bond migration of allylbenzenes under mild conditions with low catalytic loading to afford 1-propenylbenzenes. The reaction shows a unique substituent effect that is highly dependent on the distance of substituents from the allylic moiety. Thus, the reactivity of substrates bearing a methyl group is ordered in para > meta > ortho, whereas it is entirely reversed as ortho > meta > para for methoxy and chloro substituents.
- Nishiwaki, Nagatoshi,Kamimura, Ryuichiro,Shono, Kimihiro,Kawakami, Toshihiko,Nakayama, Katsuhisa,Nishino, Kohei,Nakayama, Takayuki,Takahashi, Keisuke,Nakamura, Aki,Hosokawa, Takahiro
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supporting information; experimental part
p. 3590 - 3592
(2010/08/19)
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- Molybdenum- and tungsten-catalyzed allylation of aromatic compounds with allylic esters and alcohols
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A novel method to substitute aromatic compounds with allylic groups using oxygen-containing allylic compounds in the presence of molybdenum or tungsten carbonyls under neutral conditions has been developed. The method is applicable to one step synthesis of methyl eugenol.
- Shimizu, Isao,Sakamoto, Toshiaki,Kawaragi, Saeko,Maruyama, Yooichiro,Yamamoto, Akio
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p. 137 - 138
(2007/10/03)
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- Electrophilic allylation of arenes with in situ generated allyltriarylbismuthonium compound: The Bismuth-mediated polarity inversion of allylsilanes
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Reaction of triarylbismuth difluorides 1 with allyltrimethylsilane 2 in CH2Cl2 in the presence of BF3·OEt2 at low temperature generates allyltriarylbismuthonium compound 3 as a pale yellow solution, in which aromatic hydrocarbons and ethers, triphenylphosphine, dimethyl sulfide, p-toluenesulfinate, and thiophenol are all readily allylated to afford the corresponding allyl derivatives in moderate to good yields.
- Matano, Yoshihiro,Yoshimune, Masanori,Suzuki, Hitomi
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p. 7475 - 7478
(2007/10/02)
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- Functional Selectivity in Friedel-Crafts Alkylations with Polyfunctional Reactants over Acid Zeolites
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The selective formation of allyl-substituted aromatics over acid zeolites by electrophilic substitution of the aromatics with allyl alcohols is reported.In contrast to the reaction in homogeneous phase with H2SO4, this primary product is stable and almost no consecutive reactions of allyl-substitued aromatics are observed.When allyl chloride (7) is used as alkylating agent, nearly no allyl-substituted aromatic is obtained.HCl, liberated during reaction easily isomerizes the double bond, enabling a fast consecutive reaction.This implies that functional selectivity,which is unachievable in homogeneous phase can be easily reached over microporous solid Broensted acids, provided no homogeneous acid is formed during reaction.The functional selectivity is attributed to the suppression of bimolecular side reactions and to the reduced isomerization rate of the double bond.For the electrophilic aromatic substitution, the turnover number of the acid site is about 120, confirming the true catalytic nature of this reaction.Deactivation of the catalyst is attributed to the oligomerization of an olefin, made upon hydride transfer to an allyl cation.
- Espeel, P. H.,Janssens, B.,Jacobs, P. A.
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p. 7688 - 7693
(2007/10/02)
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