10031-93-3Relevant articles and documents
Facile reaction of o-carboranyllithium reagents with functionalized alkyl halides
Cai, Jianping,Nemoto, Hiaso,Singaram, Bakthan,Yamamoto, Yoshinori
, p. 3383 - 3386 (1996)
Unlike the normal organolithium reagents, o-carboroanyllithium derivatives can tolerate many functional groups, such as ketones, nitriles and esters. This chemoselectivity is utilized in synthesizing a wide variety of o-carborane derivatives containing fu
Cobalt-catalyzed cross-coupling reactions of alkyl halides with aryl Grignard reagents and their application to sequential radical cyclization/cross-coupling reactions
Ohmiya, Hirohisa,Wakabayashi, Katsuyu,Yorimitsu, Hideki,Oshima, Koichiro
, p. 2207 - 2213 (2006)
Reactions of alkyl halides with arylmagnesium bromides in the presence of cobalt(II)(diphosphine) complexes are discussed. Treatment of 1-bromooctane with phenylmagnesium bromide with the aid of a catalytic amount of CoCl 2(dppp) [DPPP=1,3-bis(diphenylphosphino)propane] yielded octylbenzene in good yield. The reaction mechanism would include single electron transfer from an electron-rich cobalt complex to alkyl halide to generate the corresponding alkyl radical. The mechanism was justified by CoCl 2(dppe)-catalyzed [DPPE=1,2-bis(diphenylphosphino)ethane] sequential radical cyclization/cross-coupling reactions of 6-halo-1-hexene derivatives that yielded benzyl-substituted cyclopentane skeletons.
Homolytic Reactions of Ligated Boranes. Part 9. Overall Addition of Alkanes to Electron-deficient Alkenes by a Radical Chain Mechanism
Baban, Jehan A.,Roberts, Brian P.
, p. 1195 - 1200 (1988)
Methyl bromoacetate and ethyl 2-bromopropanoate are reduced by Bun3P->BH3 or Bun3P->BH2Ph to methyl acetate and ethyl propanoate, respectively, in chlorobenzene at 80-110 deg C in the presence of dibenzoyl peroxide or t-butyl perbenzoate.Amine complexes of borane or phenylborane are much less effective reducing agents.The reductions may also be initiated photochemically and are inhibited by a phenolic radical scavenger.A homolytic chain mechanism is proposed in which the phosphine-boryl radical abstracts halogen from the bromo ester and is subsequently regenerated by reaction of an α-(alkoxycarbonyl)alkyl radical with the phosphine-borane.The latter propagation step, together with halogen abstraction from RI and addition of the derived alkyl radical to the C=C bond, is also involved in the chain reaction between Bun3P->BH2Ph, an alkyl iodide, and ethyl acrylate according to equation (A); Bun3P->BH3 reacts similarly but gives lower yields of ester.Reaction (A) proceeds smoothly at 110 deg C Bun3P->BH2Ph + RI + CH2=CHCO2Et -> RCH2CH2CO2Et + Bun3P->BHIPh (A) when initiated by t-butyl perbenzoate and moderate yields of isolated esters were obtained from n-butyl iodide, cyclohexyl iodide, and 3β-iodocholest-5-ene.This last iodide gives an epimeric mixture of 3α- and 3β-esters in total isolated yield of ca. 50 percent.Similar addition reactions take place between Bun3P->BH2Ph, BunI, and diethyl vinylphosphonate or phenyl vinyl sulphone.It is concluded that Bun3P->BH3 and particularly Bun3P->BH2Ph offer promise as alternatives to tin, mercury, and germanium hydrides in radical chain reactions of synthetic value.
One-step cross-coupling reaction of functionalized alkyl iodides with aryl halides by the use of an electrochemical method
Kurono, Nobuhito,Sugita, Kazuya,Takasugi, Shingo,Tokuda, Masao
, p. 6097 - 6108 (1999)
Organozinc compounds of functionalized alkyl iodide carrying an alkoxycarbonyl, cyano or alkenyl group were prepared in high yields under mild conditions (0°C-r.t., 10min in DMF) by the reaction of iodides with an electrogenerated reactive zinc (EGZn). Cross-coupling of the organozinc compounds with various aryl halides in the presence of 5 mol% Pd(P(o- Tol)3)2Cl2 in THF gave the corresponding cross-coupled products in moderate to high yields. These cross-coupling reactions can be also achieved in one step and in one pot by the use of an electrochemical method utilizing a Pt cathode and Zn anode.
Microwave-assisted aqueous Krapcho decarboxylation
Mason, Jeremy D.,Murphree, S. Shaun
, p. 1391 - 1394 (2013)
The Krapcho decarboxylation of alkyl malonate derivatives has been adapted to aqueous microwave conditions. Various salt additives were examined, and both the cation and the anion impacted the facility of the reaction. A strong correlation was found between the pKa of the anion and the reaction rate, suggesting a straightforward base-catalyzed hydrolysis. Lithium sulfate gave the best results, obviating the need for DMSO co-solvent. Georg Thieme Verlag Stuttgart · New York.
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Kochi,Gilliom
, p. 5251,5255 (1964)
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Cu(II)-Catalyzed Olefin Migration and Prins Cyclization: Highly Diastereoselective Synthesis of Substituted Tetrahydropyrans
Ghosh, Arun K.,Nicponski, Daniel R.
, p. 4328 - 4331 (2011)
Metal-ligand complexes of Cu(OTf)2 with an appropriate bisphosphine ligand have been shown to effectively catalyze the formation of substituted tetrahydropyrans via a sequential olefin migration and Prins-type cyclization. This methodology provides convenient access to a variety of functionalized tetrahydropyrans in excellent diastereoselectivities and good to excellent yields.
Vinylation of benzylic quaternary ammonium salts catalyzed by palladium
Yi,Zhuangyu,Hongwen
, p. 245 - 247 (1995)
The palladium-catalyzed vinylation of benzylic tributylammonium salts with a variety of olefins has been studied. A possible free radical mechanism is proposed.
Synthesis of 1-(3-phenylpropyl)-4-(pyridinylmethoxy)-[1,2,4]triazolo[4,3-a] quinoxalines
Summer, Dominik,Matuszczak, Barbara
, p. 25 - 29 (2019)
Starting from 2,3-dichloroquinoxaline, a synthetic strategy for the preparation of 1-(3-phenylpropyl)-4-(pyridinylmethoxy)[1,2,4]triazolo[4,3-a]quinoxalines is described.
Ring opening of cyclopropanecarboxylates using samarium(ii) diiodide (SmI2)-HMPA-THF system
Yamashita,Okuyama,Ohhara,Kawasaki,Ohta
, p. 708 - 710 (1995)
Cyclopropane ring of 2- and 2,3-substituted cyclopropanecarboxylates (1) was regioselectively cleaved using SmI2-HMPA-THF system in the presence of tert-BuOH to give 4- and 3,4-substituted butyrates (2) in moderate to good yields.
Ruthenium pincer complex-catalyzed heterocycle compatible alkoxycarbonylation of alkyl iodides: Substrate keeps the catalyst active
Ai, Han-Jun,Wu, Xiao-Feng,Yuan, Yang
, p. 2481 - 2486 (2022/03/08)
The electron pair of the heteroatom in heterocycles will coordinate with metal catalysts and decrease or even inhibit their catalytic activity consequently. In this work, a pincer ruthenium-catalyzed heterocycle compatible alkoxycarbonylation of alkyl iodides has been developed. Benefitting from the pincer ligand, a variety of heterocycles, such as thiophenes, morpholine, unprotected indoles, pyrrole, pyridine, pyrimidine, furan, thiazole, pyrazole, benzothiadiazole, and triazole, are compatible here. This journal is
Electrochemical Tandem Olefination and Hydrogenation Reaction with Ammonia
Zhang, Xiaofeng,Jiang, Runze,Cheng, Xu
supporting information, p. 16016 - 16025 (2021/08/24)
An electrochemical Horner-Wadsworth-Emmons/hydrogenation tandem reaction was achieved using ammonia as electron and proton donors. The reaction could give two-carbon-elongated ester and nitrile from aldehyde or ketones directly. This reaction could proceed with a catalytic amount of base or even without a base. The ammonia provides both the electron and proton for this tandem reaction and enables the catalyst-free hydrogenation of an α,β-unsaturated HWE intermediate. More than 40 examples were reported, and functional groups, including heterocycles and hydroxyl, were tolerated.
Visible-light induced metal-free cascade Wittig/hydroalkylation reactions
Miao, Pannan,Li, Ruining,Lin, Xianfeng,Rao, Liangming,Sun, Zhankui
supporting information, p. 1638 - 1641 (2021/03/09)
Cascade reactions are green and powerful transformations for building multiple carbon-carbon bonds in one step. Through a relay olefination and radical addition process, we were able to develop the cascade Wittig/hydroalkylation reactions induced by visible light. This metal-free radical approach features mild conditions, robustness, and excellent functionality compatibility. It allows access to saturated C3 homologation products directly from aldehydes or ketones. The synthetic utility of this method is demonstrated by a two-step synthesis ofindolizidine 209D.
