- o-Trimethylsilylphenyllithium as a synthetic equivalent of o-halophenyllithium
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The reaction of o-trimethylsilylphenyllithium with carbonyl compounds and subsequent halogenodesilylation with ICl afforded o-iodophenylcarbinols in good yields, showing the usefulness of o-trimethylsilylphenyllithium as a synthetic equivalent of o-iodophenyl anion. The reaction via a protected o-trimethylsilylphenylcarbinol is also shown.
- Takahashi, Masaki,Hatano, Ken,Kimura, Mikio,Watanabe, Toshinari,Oriyama, Takeshi,Koga, Gen
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- One-Pot Synthesis and Conformational Analysis of Six-Membered Cyclic Iodonium Salts
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Two one-pot procedures for the construction of carbon-bridged diaryliodonium triflates and tetrafluoroborates are described. Strong Br?nsted acids enable the effective Friedel-Crafts alkylation with diversely substituted o-iodobenzyl alcohol derivatives, providing diphenylmethane scaffolds, which are subsequently oxidized and cyclized to the corresponding dibenzo[b,e]iodininium salts. Based on NMR investigations and density functional theory (DFT) calculations, we could verify the so-far-undescribed existence of two stable isomers in cyclic iodonium salts substituted with aliphatic side chains in the carbon bridge.
- Caspers, Lucien D.,Spils, Julian,Damrath, Mattis,Lork, Enno,Nachtsheim, Boris J.
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p. 9161 - 9178
(2020/08/14)
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- Highly Enantioselective Cobalt-Catalyzed Hydroboration of Diaryl Ketones
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A highly enantioselective cobalt-catalyzed hydroboration of diaryl ketones with pinacolborane was developed using chiral imidazole iminopyridine as a ligand to access chiral benzhydrols in good to excellent yields and ee. This protocol could be carried out in a gram scale under mild reaction conditions with good functional group tolerance. Chiral biologically active 3-substituted phthalide and (S)-neobenodine could be easily constructed through asymmetric hydroboration as a key step.
- Liu, Wenbo,Guo, Jun,Xing, Shipei,Lu, Zhan
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supporting information
p. 2532 - 2536
(2020/04/02)
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- Iodide as a Nucleophilic Trigger in Aryne Three-Component Coupling for the Synthesis of 2-Iodobenzyl Alcohols
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The synthetic potential of KI as the iodide source in aryne three-component coupling has been demonstrated using aldehydes as the third component. This mild and transition-metal-free coupling reaction allowed the straightforward synthesis of 2-iodobenzyl alcohols in moderate to good yields with good functional group compatibility. Moreover, KBr and KCl could be used as the nucleophilic trigger in this aryne multicomponent coupling (MCC) and N-methylisatin and CO2 could be used as the electrophilic third components.
- Bhattacharjee, Subrata,Guin, Avishek,Gaykar, Rahul N.,Biju, Akkattu T.
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supporting information
p. 4383 - 4387
(2019/06/08)
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- Nitrogen-Iodine Exchange of Diaryliodonium Salts: Access to Acridine and Carbazole
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A nitrogen-iodine exchange protocol of diaryliodonium salts with sodium azide salt is developed for general construction of significant functional acridines and carbazoles, in which introduction of nitrogen at a late stage was successfully established avoiding heteroatom incompatibility. Inorganic sodium azide served as the sole nitrogen atom source in this transformation. The diversiform functional acridines and carbazoles were comprehensively achieved through annulated diaryliodonium salts, respectively. Notably, Acridine orange (a fluorescent indicator for cell lysosomal dye) and Carprofen (a nonsteroidal anti-inflammatory drug) were efficiently established through this protocol.
- Wang, Ming,Fan, Qiaoling,Jiang, Xuefeng
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supporting information
p. 216 - 219
(2018/01/17)
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- Palladium-Catalyzed Acylations: One-Pot Synthesis of Indenones
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An efficient, one-pot synthesis of substituted indenones was accomplished starting from simple o-iodoketones and aldehydes. [Pd]-catalyzed direct acylation of o-iodoketones with aldehydes was employed as the key step. Subsequent intramolecular aldol condensation afforded the indenones. Notably, a variety of indenones were achieved. Significantly, the natural product neolignan was accomplished in one pot.
- Suchand, Basuli,Satyanarayana, Gedu
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p. 372 - 381
(2017/04/26)
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- Three-component coupling based on flash chemistry. Carbolithiation of benzyne with functionalized aryllithiums followed by reactions with electrophiles
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A flow microreactor method for three-component coupling of benzyne was developed based on flash chemistry. o-Bromophenyllithium generated from 1-bromo-2-iodobenzene and a functionalized aryllithium generated from the corresponding aryl halide were mixed at -70 °C. In the subsequent reactor o-bromophenyllithium is decomposed to generate benzyne without affecting the functionalized aryllithium at -30 °C, and carbolithiation of benzyne with the aryllithium took place spontaneously. The resulting functionalized biaryllithium was reacted with an electrophile in the subsequent reactor to give the corresponding three-component coupling product. The precise optimization of reaction conditions using the temperature-residence time mapping is responsible for the success of the present transformation. The present method has been successfully applied to the synthesis of boscalid.
- Nagaki, Aiichiro,Ichinari, Daisuke,Yoshida, Jun-Ichi
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supporting information
p. 12245 - 12248
(2014/11/08)
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- Phosphine/palladium-catalyzed syntheses of alkylidene phthalans, 3-deoxyisoochracinic acid, isoochracinic acid, and isoochracinol
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In this study we used sequential catalysis-PPh3-catalyzed nucleophilic addition followed by Pd(0)-catalyzed Heck cyclization-to construct complex functionalized alkylidene phthalans rapidly, in high yields, and with good stereoselectivities (E/Z ratios of up to 1:22). The scope of this Michael-Heck reaction includes substrates bearing various substituents around the alkylidene phthalan backbone. Applying this efficient sequential catalysis, we accomplished concise total syntheses of 3-deoxyisoochacinic acid, isoochracinic acid, and isoochracinol.
- Fan, Yi Chiao,Kwon, Ohyun
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supporting information; experimental part
p. 3264 - 3267
(2012/08/28)
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- A concise synthesis of ortho-iodobenzyl alcohols via addition of ortho-Iodophenyl grignard reagent to aldehydes and ketones
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A wide range of both secondary and tertiary ortho-iodobenzyl alcohols was synthesized via addition of ortho-iodophenyl Grignard reagents to aldehydes and ketones. Significant improvements in terms of yields were observed with ketones upon addition of CeCl3. The potential application of the target compounds as precursors for novel electrophilic trifluoromethylating reagents based on hypervalent iodine derivatives was demonstrated. Georg Thieme Verlag Stuttgart.
- Cvengro, Alcohols Jan,Stolz, Daniel,Togni, Antonio
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experimental part
p. 2818 - 2824
(2010/01/21)
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