- H3PO4 catalyzed one-pot synthesis of 1,3-diphenyl-1H-pyrazole-4-carbaldehyde to novel 1,3-diphenyl-1H-pyrazole-4-carbonitrile
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Abstract: One-pot condensation of pyrazole-4-aldehydes and hydroxylamine hydrochloride to form the corresponding oxime using formic acid as a medium and further dehydration of oxime using a catalytic amount of orthophosphoric acid to afford novel pyrazole-4-carbonitrile. This protocol serves as an ortho-phosphoric acid-catalyzed one-pot conversion of aldehyde to nitrile. Most remarkable features of this method are metal-free, cost-effective, atom efficiency with excellent yield (98–99%). This process will serve as a robust and scalable tool for the synthesis of valuable and versatile precursor (nitriles). This precursor will pave the way for the synthesis of various medicinally important valuable compounds. Graphic abstract: [Figure not available: see fulltext.].
- Choudhare, Tukaram S,Netankar, Prashant D,Shirsath, Sagar E,Wagare, Devendra S
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- Electrochemical Tandem Olefination and Hydrogenation Reaction with Ammonia
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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.
- Zhang, Xiaofeng,Jiang, Runze,Cheng, Xu
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p. 16016 - 16025
(2021/08/24)
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- HCl·DMPU-assisted one-pot and metal-free conversion of aldehydes to nitriles
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We report an efficient HCl·DMPU assisted one-pot conversion of aldehydes into nitriles. The use of HCl·DMPU as both an acidic source as well as a non-nucleophilic base constitutes an environmentally mild alternative for the preparation of nitriles. Our protocol proceeds smoothly without the use of toxic reagents and metal catalysts. Diverse functionalized aromatic, aliphatic and allylic aldehydes incorporating various functional groups were successfully converted to nitriles in excellent to quantitative yields. This protocol is characterized by a broad substrate scope, mild reaction conditions, and high scalability. This journal is
- Hammond, Gerald B.,Mudshinge, Sagar R.,Potnis, Chinmay S.,Xu, Bo
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supporting information
p. 4161 - 4164
(2020/07/14)
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- Synthesis, characterization, catalytic and biological application of half-sandwich ruthenium complexes bearing hemilabile (κ2-: C, S)-thioether-functionalised NHC ligands
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A series of cationic Ru(ii)(η6-p-cymene) complexes with thioether-functionalised N-heterocyclic carbene ligands have been prepared and fully characterized. Steric and electronic influence of the R thioether substituent on the coordination of the sulfur atom was investigated. The molecular structure of three of them has been determined by means of X-ray diffractrometry and confirmed the bidentate (κ2-C,S) coordination mode of the ligand. Interestingly, only a single diastereomer, as an enantiomeric couple, was observed in the solid state for complexes 1c, 1i and 1j. DFT calculations established a low energy inversion barrier between the two diastereomers through a sulfur pyramidal inversion pathway with R donating group while a dissociative/associative mechanism is more likely with R substituents that contain electron withdrawing group, thus suggesting that the only species observed by the 1H-NMR correspond to an average resonance position of a fluxional mixtures of isomers. All these complexes were found to catalyse the oxydant-free double dehydrogenation of primary amine into nitrile. Ru complex bearing NHC-functionalised S-tBu group was further investigated in a wide range of amines and was found more selective for alkyl amine substrates than for benzylamine derivatives. Finally, preliminary results of the biological effects on various human cancer cells of four selected Ru complexes are reported.
- Achard, Thierry,Bellemin-Laponnaz, Stéphane,Chen, Weiguang,Egly, Julien,Maisse-Francois, Aline,Poblador-Bahamonde, Amalia I.
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supporting information
p. 3243 - 3252
(2020/03/19)
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- Selective Transformations of Triglycerides into Fatty Amines, Amides, and Nitriles by using Heterogeneous Catalysis
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The use of triglycerides as an important class of biomass is an effective strategy to realize a more sustainable society. Herein, three heterogeneous catalytic methods are reported for the selective one-pot transformation of triglycerides into value-added chemicals: i) the reductive amination of triglycerides into fatty amines with aqueous NH3 under H2 promoted by ZrO2-supported Pt clusters; ii) the amidation of triglycerides under gaseous NH3 catalyzed by high-silica H-beta (Hβ) zeolite at 180 °C; iii) the Hβ-promoted synthesis of nitriles from triglycerides and gaseous NH3 at 220 °C. These methods are widely applicable to the transformation of various triglycerides (C4–C18 skeletons) into the corresponding amines, amides, and nitriles.
- Jamil, Md. A. R.,Siddiki, S. M. A. Hakim,Touchy, Abeda Sultana,Rashed, Md. Nurnobi,Poly, Sharmin Sultana,Jing, Yuan,Ting, Kah Wei,Toyao, Takashi,Maeno, Zen,Shimizu, Ken-ichi
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p. 3115 - 3125
(2019/04/26)
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- Easy Ruthenium-Catalysed Oxidation of Primary Amines to Nitriles under Oxidant-Free Conditions
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A dehydrogenation of primary amine to give the corresponding nitrile under oxidant- and base-free conditions catalysed by simple [Ru(p-cym)Cl2]2 with no extra ligand is reported. The system is highly selective for alkyl amines, whereas benzylamine derivatives gave the nitrile product together with the imine in a ratio ranging from 14:1 to 4:1 depending on the substrate. Preliminary mechanistic investigations have been performed to identify the key factors that govern the selectivity.
- Achard, Thierry,Egly, Julien,Sigrist, Michel,Maisse-Fran?ois, Aline,Bellemin-Laponnaz, Stéphane
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supporting information
p. 13271 - 13274
(2019/10/21)
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- Ru@UiO-66(Ce) catalyzed acceptorless dehydrogenation of primary amines to nitriles: The roles of Lewis acid-base pairs in the reaction
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UiO-66(Ce)-encapsulated ruthenium nanoparticles (Ru@UiO-66(Ce)) was designed and used for dehydrogenation of primary amines to nitriles in water without any hydrogen acceptors and additives. Introduction of metal Ru to UiO-66(Ce) contributes to the formation of Lewis acid-base pairs on the catalyst owing to the metal-support interaction, acting as active sites for activation of amines and transfer of hydrogen. Ab initio calculation results further confirm the roles of Lewis acid-base pairs in the reaction.
- Lu, Guo-Ping,Li, Xinxin,Zhong, Lixiang,Li, Shuzhou,Chen, Fei
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supporting information
p. 5386 - 5393
(2019/10/11)
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- Transforming Olefins into γ,δ-Unsaturated Nitriles through Copper Catalysis
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We have developed a strategy to transform olefins into homoallylic nitriles through a mechanism that combines copper catalysis with alkyl nitrile radicals. The radicals are easily generated from alkyl nitriles in the presence of the mild oxidant di-tert-butyl peroxide. This cross-dehydrogenative coupling between simple olefins and alkylnitriles bears advantages over the conventional use of halides and toxic cyanide reagents. With this method, we showcase the facile synthesis of a flavoring agent, a natural product, and a polymer precursor from simple olefins.
- Wu, Xuesong,Riedel, Jan,Dong, Vy M.
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supporting information
p. 11589 - 11593
(2017/09/11)
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- Steric effect of carboxylic acid ligands on Pd-catalyzed C-H activation reactions
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Various carboxylic acids with different substitution patterns were used as ligands in intra- and intermolecular Pd-catalyzed C-H activation reactions to investigate steric effect of the ligands. Bulky carboxylic acids suppress deactivation of Pd catalysts
- Fujihara, Tetsuaki,Yoshida, Atsushi,Satou, Motoi,Tanji, Yutaka,Terao, Jun,Tsuji, Yasushi
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- Catalytic Hydrogen Production by Ruthenium Complexes from the Conversion of Primary Amines to Nitriles: Potential Application as a Liquid Organic Hydrogen Carrier
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The potential application of the primary amine/nitrile pair as a liquid organic hydrogen carrier (LOHC) has been evaluated. Ruthenium complexes of formula [(p-cym)Ru(NHC)Cl2] (NHC=N-heterocyclic carbene) catalyze the acceptorless dehydrogenation of primary amines to nitriles with the formation of molecular hydrogen. Notably, the reaction proceeds without any external additive, under air, and under mild reaction conditions. The catalytic properties of a ruthenium complex supported on the surface of graphene have been explored for reutilization purposes. The ruthenium-supported catalyst is active for at least 10 runs without any apparent loss of activity. The results obtained in terms of catalytic activity, stability, and recyclability are encouraging for the potential application of the amine/nitrile pair as a LOHC. The main challenge in the dehydrogenation of benzylamines is the selectivity control, such as avoiding the formation of imine byproducts due to transamination reactions. Herein, selectivity has been achieved by using long-chain primary amines such as dodecylamine. Mechanistic studies have been performed to rationalize the key factors involved in the activity and selectivity of the catalysts in the dehydrogenation of amines. The experimental results suggest that the catalyst resting state contains a coordinated amine.
- Ventura-Espinosa, David,Marzá-Beltrán, Aida,Mata, Jose A.
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p. 17758 - 17766
(2016/11/28)
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- Suzuki-miyaura cross-coupling reactions of unactivated alkyl halides catalyzed by a nickel pincer complex
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A nickel(II) pincer complex, [(MeN2N)Ni-Cl], was used to catalyze alkyl-alkyl and alkyl-aryl Suzuki-Miyaura coupling reactions of unactivated alkyl halides. The coupling of 9-alkyl-9-borabicyclo[3.3.1]nonane and 9-phenyl-9-borabicyclo[3.3.1]nonane reagents with alkyl halides was achieved in modest to good yields. The reactions tolerated a variety of useful functional groups including ester, ether, furan, thioether, acetal, and Boc groups. Georg Thieme Verlag Stuttgart, New York.
- Di Franco, Thomas,Boutin, Nicolas,Hu, Xile
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p. 2949 - 2958
(2013/11/06)
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- Highly practical synthesis of nitriles and heterocycles from alcohols under mild conditions by aerobic double dehydrogenative catalysis
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A mild, aerobic, catalytic process for obtaining nitriles directly from alcohols and aqueous ammonia is described. The reaction proceeds via a dehydrogenation cascade mediated by catalytic CuI, bpy, and TEMPO in the presence of O2. The substrate scope is broad including various functionalized aromatic and aliphatic alcohols. This protocol enabled the one-pot synthesis of various biaryl heterocycles directly from commercially available alcohols.
- Yin, Weiyu,Wang, Chengming,Huang, Yong
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supporting information
p. 1850 - 1853
(2013/06/04)
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- Transformations of 1-(oxiranylmethyl)-1,2,3-triazoles into 2-(Oxiranylmethyl)-1,2,3-triazoles and alkanenitriles
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New reactions for the transformation of 1-(oxiranylmethyl)-1,2,3-triazoles into 2-(oxiranylmethyl)-1,2,3-triazoles or alkanenitriles were established. Successive treatment of the substrate with triflic acid and t-BuOH afforded 4,6-dihydro-5-hydroxy-1,3a,6a-triazapentalene derivative. Under the influence of NaH, the bicyclic compound was converted into a 2-(oxiranylmethyl)-1,2,3- triazole or an alkanenitrile. The reaction pathway depends on the substituent pattern of the epoxide side chain. Georg Thieme Verlag Stuttgart New York.
- Osawa, Ayumi,Mera, Akane,Namba, Kosuke,Tanino, Keiji
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p. 207 - 210
(2013/02/25)
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- A chemoselective, one-pot transformation of aldehydes to nitriles
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This paper describes a procedure for direct conversion of aldehydes to nitriles using O-(diphenylphosphinyl)hydroxylamine (DPPH). Aldehydes are smoothly transformed to their corresponding nitriles by heating with DPPH in toluene. The reaction can be accomplished in the presence of alcohol, ketone, ester, or amine functionality.
- Laulhe, Sebastien,Gori, Sadakatali S.,Nantz, Michael H.
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p. 9334 - 9337,4
(2012/12/12)
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- A chemoselective, one-pot transformation of aldehydes to nitriles
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This paper describes a procedure for direct conversion of aldehydes to nitriles using O-(diphenylphosphinyl)hydroxylamine (DPPH). Aldehydes are smoothly transformed to their corresponding nitriles by heating with DPPH in toluene. The reaction can be accomplished in the presence of alcohol, ketone, ester, or amine functionality.
- Laulhé, Sébastien,Gori, Sadakatali S.,Nantz, Michael H.
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p. 9334 - 9337
(2013/01/15)
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- Fe5C2 nanoparticles: A facile bromide-induced synthesis and as an active phase for Fischer-Tropsch synthesis
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Iron carbide nanoparticles have long been considered to have great potential in new energy conversion, nanomagnets, and nanomedicines. However, the conventional relatively harsh synthetic conditions of iron carbide hindered its wide applications. In this
- Yang, Ce,Hou, Yanglong,Zhao, Huabo,Ma, Ding
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p. 15814 - 15821,8
(2020/08/24)
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- Facile transformation of esters to nitriles
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Various esters were efficiently converted into the corresponding nitriles in good yields by the treatment with sodium diisobutyl-tert-butoxyaluminium hydride (SDBBA-H), followed by treatment with molecular iodine in aq ammonia. The present one-pot method is very efficient and practical for the conversion of various aromatic and aliphatic esters into the corresponding nitriles.
- Suzuki, Yusuke,Moriyama, Katsuhiko,Togo, Hideo
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experimental part
p. 7956 - 7962
(2011/11/07)
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- Direct transformation of N,N-disubstituted amides and isopropyl esters to nitriles
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Various N,N-dimethyl amides, N-methoxy-N-methyl amides, and isopropyl esters were smoothly transformed into the corresponding nitriles in good to moderate yields by the treatment with diisobutylaluminium hydride, followed by treatment with molecular iodine in aq ammonia. The present reactions are novel one-pot and practical methods for the transformation of N,N-disubstituted amides and isopropyl esters into nitriles, through the formation of hemiaminal O-AlBu2 and hemiacetal O-AlBu2, respectively.
- Suzuki, Yusuke,Yoshino, Takumi,Moriyama, Katsuhiko,Togo, Hideo
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experimental part
p. 3809 - 3814
(2011/06/25)
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- A facile and efficient one-pot synthesis of nitriles from carboxylic acids
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Direct transformation of aliphatic carboxylic acids to the corresponding nitriles can be easily performed with acetonitrile in the presence of sulfuric acid. Georg Thieme Verlag Stuttgart.
- Mlinari?-Majerski, Kata,Margeta, Renato,Veljkovi?, Jelena
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p. 2089 - 2091
(2007/10/03)
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- Dehydrogenation of amines to nitriles in aqueous micelles
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An aqueous reaction medium, based on a surfactant solution of dimethyldodecylamine N-oxide (DDAO) has been developed for the oxidative dehydrogenation of primary amines using NiSO4 as catalyst and K 2S2O8 as oxidant. This reaction medium enhances the rate of the reaction relative to other media previously reported in the literature, which are also toxic. The reactions of various aliphatic and cyclic amines have been investigated and gave nitriles with yields of >90% in mild conditions. The aqueous surfactant solution and reagents were recycled for future use. Wiley-VCH Verlag GmbH & Co. KGaA, 2005.
- Biondini, Daniele,Brinchi, Lucia,Germani, Raimondo,Goracci, Laura,Savelli, Gianfranco
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p. 3060 - 3063
(2007/10/03)
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- Highly Convenient, One-Pot Synthesis of Nitriles from Aldehydes Using the NH2OH·HCl/NaI/MeCN System
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Direct transformation of both aliphatic and aromatic aldehydes to the corresponding nitriles, can be easily performed by the reaction of an aldehyde with a slight excess of hydroxylamine hydrochloride, in refluxing acetonitrile and in the presence of 0.5 equivalents of sodium iodide as catalyst.
- Ballini, Roberto,Fiorini, Dennis,Palmieri, Alessandro
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p. 1841 - 1843
(2007/10/03)
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- An efficient one-pot synthesis of nitriles from carboxylic acids without solvent under microwave irradiation
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Nitriles were prepared from alkyl and aryl carboxylic acids in dry media conditions, under microwave irradiation. Heating of the carboxylic acid, urea and amidosulfonic acid adsorbed on alumina support in a microwave oven affords nitriles in 20-93% yields.
- Juncai, Feng,Bin, Liu,Yang, Lhi,Changchuan, Li
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p. 4545 - 4548
(2007/10/03)
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- Reductive decyanation of α-cyano and α-alkoxycarbonyl substituted nitriles promoted by samarium(II) iodide
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Decyanation of geminal dinitriles and α-alkoxycarbonyl substituted nitriles promoted by samarium(II) iodide has been efficiently achieved. This method has advantages over the previously known radical route using tin hydride with respect to applicable substrates and the reaction temperature employed. This decyanation could broaden the synthetic applicability of the nitrile derivatives.
- Kang,Hong,Cho,Koh
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p. 7661 - 7664
(2007/10/02)
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- EVALUATION OF TRIBUTYLGERMANIUM HYDRIDE AS A REAGENT FOR THE REDUCTIVE ALKYLATION OF ACTIVE OLEFINS WITH ALKYL HALIDES
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The reductive alkylation of acrylonitrile and of 2-cyclohexen-1-one by alkyl halides using tributylgermanium hydride was systematically evaluated.The performance of the germanium reagent was compared to that of the more commonly employed tributyltin hydride.For certain applications thegermanium reagent afforded improved yields without the use of large excess olefin concentrations.Disadvantages of the germanium reagent include a tendency to hydrogermylate active terminal olefins and a general low reactivity towards alkyl halide substrates.The following series of six other triorganotin and triorganogermanium hydrides were also briefly screened for possible application to reductive alkylations: trimesityltin hydride, trimesitylgermanium hydride, triphenyltin hydride, triphenylgermanium hydride, trineopentyltin hydride, and tricyclohexylgermanium hydride.
- Pike, Philip,Hershberger, Susan,Hershberger, James
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p. 6295 - 6304
(2007/10/02)
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- ALKYL ADDITIONS TO ACTIVE OLEFINS BY TRIBUTYLGERMANIUM HYDRIDE REDUCTION OF ALKYL HALIDES.
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Tri(n-butyl)germanium hydride is a superior reagent for the reductive addition of alkyl halides to active olefins.
- Pike, Philip,Hershberger, Susan,Hershberger, James
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p. 6289 - 6290
(2007/10/02)
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