- Transition-metal-catalyzed benzylation of arenes and heteroarenes
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Friedel-Crafts-type benzylation of various aromatic and heteroaromatic compounds with benzylic acetates, alcohols, and carbonates was promoted under mild reaction conditions by a series of Rh, Ir, Pd, and Pt catalysts (see scheme; R1 = H, Me; R2 = H, Cl, MeO; R3 = H, Ac, CO2Me). The desired products were obtained in high yields and with high selectivities.
- Mertins, Kristin,Iovel, Irina,Kischel, Jette,Zapf, Alexander,Beller, Matthias
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- A general copper-catalyzed radical C(sp3)?C(sp2) cross-coupling to access 1,1-diarylalkanes under ambient conditions
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A general copper-catalyzed C(sp3)?C(sp2) cross-coupling of (hetero)benzyl bromides with the air- and moisture-stable aryl nucleophiles has been developed, providing a facile access to pharmaceutically useful 1,1-di(hetero)arylalkane and 1-aryl-1-heteroarylalkane scaffolds. Critical to the success is the utilization of a proline-based N,N,P-ligand to enhance the reducing capability of copper, thus easily converting benzyl bromides to the corresponding radical species via a single-electron transfer process under ambient conditions. The reaction features a broad substrate scope, covering (hetero)arylboronate esters, oxadiazoles, and benzo[d]oxazoles, as well as primary and secondary (hetero)benzyl bromides with excellent functional group tolerance.
- Su, Xiao-Long,Jiang, Sheng-Peng,Ye, Liu,Xu, Guo-Xing,Chen, Ji-Jun,Gu, Qiang-Shuai,Li, Zhong-Liang,Liu, Xin-Yuan
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supporting information
(2021/05/06)
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- [C^N]-Alkenyl Gold(III) Complexes by Proximal Ring-Opening of (2-Pyridyl)alkylidenecyclopropanes: Mechanistic Insights
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Pyridine-substituted alkylidenecyclopropanes (Py-ACPs) react with gold(III) salts under mild reaction conditions through an unprecedented, proximal ring-opening pathway, to generate highly appealing, catalytically active pyridine alkenyl [C^N]-gold(III) species. Mechanistic studies reveal that the activation of the C?C bond of the ACP takes place through an unusual concerted, σ-bond metathesis type-process.
- González, Jorge A.,López, Fernando,Mascare?as, José Luis,Nevado, Cristina,Verdugo, Felipe
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supporting information
p. 20049 - 20054
(2020/09/09)
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- Iron-catalyzed arylation of aromatic ketones and aldehydes mediated by organosilanes
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A simple and efficient iron-catalyzed method for arylation of aromatic carbonyl compounds is reported. The use of 4-% FeCl3 or Fe(acac) 3 as the catalyst, in combination with a slight excess of chlorotrimethylsilane and triethylsilane, chlorination of benzylic ketones and aldehydes with subsequent Friedel-Crafts alkylation of arenes is achieved. Although the method is limited by the general constraints associated with Friedel-Crafts alkylation reactions, robust applications for the synthesis of pharmaceutical intermediates and so on can be envisioned. A robust one-pot, iron-catalyzed chlorination Friedel-Crafts alkylation reaction of benzylic carbonyl compounds, mediated by chlorotrimethylsilane and triethylsilane, has been developed to yield substituted diaryl and triaryl building blocks. Copyright
- Savela, Risto,Majewski, Marcin,Leino, Reko
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p. 4137 - 4147
(2014/07/08)
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- Synthesis of diarylmethanes via a Friedel-Crafts benzylation using arenes and benzyl alcohols in the presence of triphenylphosphine ditriflate
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Triphenylphosphine ditriflate (TPPD) was found to be an efficient promoter for the Friedel-Crafts benzylation of arenes with benzyl alcohols in CH 2Cl2 at room temperature. The good yields, the 1:1 molar ratio of arene and benzyl alcohol, the benzylation of chlorobenzene as a nonactivated aromatic compound at room temperature, and no by-product formation are the main advantages of this procedure.
- Khodaei, Mohammad Mehdi,Nazari, Ehsan
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experimental part
p. 5131 - 5135
(2012/09/22)
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- Iron(iii)-based ionic liquid-catalyzed regioselective benzylation of arenes and heteroarenes
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An easily prepared Fe(iii)-derived Lewis acid ionic liquid ([C 4mim][FeCl4]), being comprised of 1-butyl-3-methyl imidazolium cation and tetrachloroferrate anion, was found to be an efficient, recyclable catalyst for benzylation of various arenes/heteroarenes into the diarylmethanes derivatives under mild reaction conditions without utilization of additional organic solvent. Interestingly, the acidity of [C 4mim][FeCl4] could account for its catalytic activity in promoting the Lewis acid-catalyzed alkylation. Notably, this type of Fe(iii)-based ionic liquid (IL) shows excellent stability, and could be easily recovered, and reused for five times without significant loss of its catalytic activity.
- Gao, Jian,Wang, Jin-Quan,Song, Qing-Wen,He, Liang-Nian
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p. 1182 - 1186
(2011/06/25)
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- Highly efficient gold(III)-catalyzed intermolecular hydroarylation of unactivated alkenes with arenes under mild conditions
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A simple and efficient method for functionalization of electron-rich arenes and heteroarenes with unactivated alkenes by Au(III)-catalyzed intermolecular hydroarylation under mild reaction conditions was developed. This method features a short reaction time (5 h) under mild conditions and has a broad substrate scope, including electron-rich arenes and heteroarenes, terminal and internal substituted aryl alkenes, and unactivated aliphatic alkenes.
- Xiao, Ya-Ping,Liu, Xin-Yuan,Che, Chi-Ming
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experimental part
p. 494 - 501
(2009/06/06)
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- A novel InCl3/SiO2-catalyzed hydroarylation of arenes with styrenes under solvent-free conditions
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A novel InCl3/SiO2-catalyzed hydroarylation of various styrenes with arenes has been developed. The reaction can be carried out under solvent-free conditions to afford a series of 1,1-diarylalkanes in high yields and with good regioselectivities. The catalyst can be reused six times without obvious loss of catalytic activity. Georg Thieme Verlag Stuttgart.
- Sun, Gaojun,Sun, Huayin,Wang, Zhiyong,Zhou, Ming-Ming
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experimental part
p. 1096 - 1100
(2009/04/04)
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- Secondary benzylation with benzyl alcohols catalyzed by a high-valent heterobimetallic Ir-Sn complex
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(Chemical Equation Presented) A highly efficient secondary benzylation procedure has been demonstrated using a high-valent heterobimetallic complex [Ir2(COD)2(SnCls)2(Cl)2(μ-Cl) 2] 1 as the catalyst in 1,2-dichloroethane to afford the corresponding benzylated products in moderate to excellent yields. The reaction was performed not only with carbon nucleophiles (arenes and heteroarenes) but also with oxygen (alcohol), nitrogen (amide and sulfonamide), and sulfur (thiol) nucleophiles. Mechanistic investigation showed the intermediacy of the ether in this reaction. An electrophilic mechanism is proposed from Hammett correlation.
- Podder, Susmita,Choudhury, Joyanta,Roy, Sujit
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p. 3129 - 3132
(2008/02/07)
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- Highly efficient iodine-catalyzed hydroarylation of arenes with styrenes
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Iodine mediates the hydroarylation of styrenes with arenes and heteroarenes to afford 1,1-diarylalkanes in good to high yields. Details regarding the substrate scope and selectivity of this hydroarylation reaction are discussed.
- Chu, Cheng-Ming,Huang, Wan-Ju,Liu, Ju-Tsung,Yao, Ching-Fa
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p. 6881 - 6885
(2008/02/12)
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- An effective bismuth-catalyzed benzylation of arenes and heteroarenes
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A highly efficient Bi(OTf)3-catalyzed benzylation of arenes and heteroarenes has been developed. The mild reaction conditions, high yields, operational simplicity and practicability, broad scope, and remarkably low catalyst loading render this environment friendly process an attractive approach to diarylmethane derivatives. The extension to an intramolecular variant of this procedure provides a valuable route to substituted fluorenes.
- Rueping, Magnus,Nachtsheim, Boris J.,Ieawsuwan, Winai
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p. 1033 - 1037
(2007/10/03)
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- An efficient and general iron-catalyzed arylation of benzyl alcohols and benzyl carboxylates
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(Chemical Equation Presented) Green grow the diarylmethanes: Substituted arenes and heteroarenes can be easily benzylated in the presence of inexpensive and relatively nontoxic metal salts such as FeCl3 (see scheme). This arylation method with benzyl alcohols is a state-of-the-art green route to diarylmethanes as water is the only by-product.
- Iovel, Irina,Mertins, Kristin,Kischel, Jette,Zapf, Alexander,Beller, Matthias
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p. 3913 - 3917
(2007/10/03)
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