- Conversion of 3,3,3-Trisubstituted Prop-1-ynes with tert-Butylhydrazine into 3,3,3-Trisubstituted Propionitriles Catalyzed by TpRh(C2H4)2/P(2-furyl)3
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The combination of TpRh(C2H4)2 (Tp = tris(pyrazol-1-yl)borate) and P(2-furyl)3 catalyzes the reaction of tertiary alkyl-substituted alkynes with tert-butylhydrazine, leading to the formation of 3,3,3-trisubstituted propionitrile derivatives. This reaction system is applicable to 1,1-disubstituted propargyl alcohols and amines to afford the corresponding β-cyanohydrins and β-amino nitriles, respectively. The catalytic cycle involves the formation of a vinylidenerhodium complex as a key intermediate.
- Fukumoto, Yoshiya,Tamura, Yuto,Iyori, Yasuaki,Chatani, Naoto
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p. 3161 - 3167
(2016/05/19)
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- Nucleophilic addition of α-(dimethylsilyl)nitriles to aldehydes and ketones
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α-Alkylated (dimethylsilyl)acetonitriles (Me2HSiCR 3R4CN) react spontaneously with aldehydes in DMSO to give β-hydroxynitriles in good to high yields. The addition to ketones is effectively promoted by using MgCl2/su
- Jinzaki, Takaaki,Arakawa, Mitsuru,Kinoshita, Hidenori,Ichikawa, Junji,Miura, Katsukiyo
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supporting information
p. 3750 - 3753
(2013/08/23)
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- Reaction of the electrogenerated cyanomethyl anion with carbonyl compounds: A clean and safe synthesis of β-hydroxynitriles
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The electrogenerated cyanomethyl anion reacts with carbonyl compounds to yield the corresponding β-hydroxymtriles in moderate to high yields. The reported methodology is very clean and safe, avoiding the use of any classical base or catalyst.
- Bianchi, Gabriele,Feroci, Marta,Rossi, Leucio
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experimental part
p. 3863 - 3866
(2010/01/11)
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- Catalytic cyanomethylation of carbonyl compounds and imines with highly basic phosphine
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A highly basic phosphine, tris(2,4,6-trimethoxy phenyl)phosphine (TTMPP), catalyzes cyanomethylation using trimethylsilylacetonitrile (TMSCH2CN) to give the corresponding products in good to high yields, with both carbonyl compounds and imines.
- Matsukawa, Satoru,Kitazaki, Eri
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p. 2982 - 2984
(2008/09/20)
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- Metalated nitriles: Organolithium, -magnesium? and -copper exchange of α-halonitriles
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(Chemical Equation Presented) α-Halonitriles react with alkyllithium, organomagnesium, and lithium dimethylcuprate reagents generating reactive, metalated nitriles. The rapid halogen-metal exchange with alkyllithium and Grignard reagents allows selective exchange in the presence of reactive carbonyl electrophiles, including aldehydes, providing a high-yielding alkylation protocol. Lithiated and magnesiated nitriles react with propargyl bromide by SN2 displacement whereas organocopper nitriles react by S N2′ displacement, correlating with the formation of a C-metalated nitrile.
- Fleming, Fraser F.,Zhang, Zhiyu,Liu, Wang,Knochel, Paul
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p. 2200 - 2205
(2007/10/03)
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- Metalated Nitriles: Halogen - Metal Exchange with α-Halonitriles
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(Equation presented) α-Halonitriles react with organometallic reagents in a facile halogen-metal exchange. The halogen-metal exchange is extremely fast with Grignard and alkyllithium reagents, generating metalated nitriles in situ with aldehyde, ketone, a
- Fleming, Fraser F.,Zhang, Zhiyu,Knochel, Paul
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p. 501 - 503
(2007/10/03)
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- Direct conversion of α,β-unsaturated nitriles into cyanohydrins using Mn(dpm)3 catalyst, dioxygen and phenylsilane
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Treatment of α,β-unsaturated nitriles with Mn(dpm)3 (3 mol%), PhSiH3 in isopropyl alcohol in the presence of oxygen resulted in reduction and α- and β-hydroxylation.
- Magnus, Philip,Scott, David A.,Fielding, Mark R.
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p. 4127 - 4129
(2007/10/03)
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- SmI2-mediated nitrile aldol reaction
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The SmI2-mediated coupling of α-bromoacetonitrile and α- bromopropionitrile with aliphatic ketones and aldehydes produces β- hydroxynitriles in good yields. Reactions typically proceed with little diastereoselectivity, but selectivity enhanceme
- Caracoti, Andrei,Flowers II, Robert A.
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p. 3039 - 3041
(2007/10/03)
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- P(RNCH2CH2)3N-Catalyzed synthesis of β-hydroxy nitriles
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We herein report the successful synthesis of β-hydroxy nitriles in very good to excellent yields from aldehydes and ketones in a simple reaction that is promoted by strong nonionic bases of the title type. The reaction occurs in the presence of magnesium salts which activate the carbonyl group and stabilizes the enolate thus produced.
- Kisanga, Philip,McLeod, Dale,D'Sa, Bosco,Verkade, John
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p. 3090 - 3094
(2007/10/03)
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- Aryl halides as precursors of electrogenerated bases. Utilization in coupling reactions of acetonitrile with various electrophilic compounds
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An electrochemical alternative to classical cyanomethylation is possible by using electrogenerated bases (EGBs), obtained by electroreduction of aryl halides in an undivided cell fitted with a cadmium coated cathode and a sacrificial magnesium anode. Acetonitrile is used both as solvent and as hydrogen-active compound. A coupling reaction with various electrophilic compounds was carried out. When the electrophilic compound was present from the beginning of the electrolysis, the expected coupling product with the cyanomethyl anion was obtained. If the electrophilic compound was added only after complete electrolysis of the aryl halide, dimerization of the cyanomethyl anion and a coupling reaction between the dimer anion and the electrophilic compound were observed.
- Barhdadi, Rachid,Gal, Jacques,Heintz, Monique,Troupel, Michel,Perichon, Jacques
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p. 5091 - 5098
(2007/10/02)
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- Electroorganic Chemistry. 140. Electroreductively Intra- and Intermolecular Couplings of Ketones with Nitriles
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Electroreduction of γ- and δ-cyano ketones in i-PrOH with Sn cathode gave α-hydroxy ketones and their dehydroxylated ketones as the intramolecularly coupled products.Guaiazulene, (-)-valeranone, polyquinanes, dihydrojasmone, methyl dihydrojasmonate, and rosaprostol have been synthesized by utilizing this electroreductive intramolecular coupling of γ- and δ-cyano ketones in one of the key steps.Similarly, electroreduction of a mixture of ketone and nitrile gave the corresponding intermolecularly coupled product.The product obtained by the electroreductive intermolecular coupling of (+)-dihydrocarvone with acetonitrile has been found to be the precursor of an effective chiral ligand for the enantioselective addition of diethylzinc to aldehydes.
- Shono, Tatsuya,Kise, Naoki,Fujimoto, Taku,Tominaga, Naoto,Morita, Hiroshi
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p. 7175 - 7187
(2007/10/02)
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- A catalyst for asymmetric induction
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Catalysts for producing optically active cyanohydrins by addition of hydrogen cyanide to aldehydes comprising a titanium (IV) alkoxide and a dipeptide derivative of formula (I) wherein R1 is isopropyl, isobutyl, sec-butyl, tert-butyl, methyl, benzyl or phenyl, R3 is lower alkoxy, hydroxyl or mono- or di-lower alkylamino, and either R4 is hydrogen and R2 is benzyl, indol-3-ylmethyl, isopropyl, isobutyl, or phenyl, or R2 and R4 together form -CH2-CH=CH- or -CH=CH-CH2-, R5, R6, R7 and R8 are the same or different and each is hydrogen, halogen, lower alkyl or lower alkoxy, or R5 and R6 or R6 and R7, or R7 and R8 together form -CH=CH-CH=CH- or -OCH2O-, and * denotes an asymmetric carbon atom having an absolute configuration of S or R.
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- INDIRECT ELECTROREDUCTION OF α,β-EPOXY CARBONYL COMPOUNDS AND THEIR ANALOGUES BY USE OF A (PhSe)2/SACRIFICAL ANODE SYSTEM
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Indirect electroreductive transformations of α,β-epoxy carbonyl compounds 1 mediated by diphenyl diselenide ((PhSe)2) as a recyclable reagent to their β-hydroxy derivatives 2 in 80-90percent yields were achieved in an undivided cell by use of a sacrificia
- Inokuchi, Tsutomu,Kusumoto, Masahiko,Sugimoto, Tatsuya,Tanaka, Hideo,Torii, Sigeru
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p. 271 - 276
(2007/10/02)
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- Metal Exchange between an Electrogenerated Organonickel Species and Zinc Halide: Application to an Electrochemical, Nickel-Catalyzed Reformatsky Reaction
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The mechanism of the electroreductive coupling of α-chloro esters or α-chloro nitriles with carbonyl compounds by the means of a sacrificial zinc anode and a nickel catalyst was elucidated by electroanalytical techniques.The mechanism involved reduction of a Ni(II) complex to a Ni(0) complex, oxidative addition of the α-chloro ester to the Ni(0) complex, and a Zn(II)/Ni(II) exchange, leading to an organozinc Reformatsky reagent.The electrosynthesis of various β-hydroxy esters, β-hydroxy nitriles, and 2,3-epoxy esters was successfully achieved under extremely mild conditions.
- Conan, Annie,Sibille, Soline,Perichon, Jacques
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p. 2018 - 2024
(2007/10/02)
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- Easy Direct Stereo- and Regioselective Formation of β-Hydroxy Nitriles by Reaction of 1,2-Epoxides with Potassium Cyanide in the Presence of Metal Salts
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A simple efficient, anti stereoselective, and highly regioselective method for the synthesis of β-hydroxy nitriles by the direct opening of 1,2-epoxides with KCN in acetonitrile, in the presence of metal salts, is described.This new method appears to be competitive with the other methods previously reported. Key words: β-hydroxy nitriles; epoxide opening reactions; regioselectivity; catalysts.
- Chini, Marco,Crotti, Paolo,Favero, Lucilla,Macchia, Franco
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p. 4775 - 4778
(2007/10/02)
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- REFORMATSKY REACTION USING Zn/Ag COUPLE
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The Reformatsky reaction is easy to run in ethereal solvents in the presence of Zn/Ag couple.From methyl γ-bromocrotonate and krtones, remified esters are fromed in refluxing Et2O, linear ones in refluxing THF.
- Bortolussi, Michel,Seyden-Penne, Jacqueline
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p. 2355 - 2362
(2007/10/02)
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- Process for the preparation of N-(2-(cyclo-hexen-1-yl)ethyl)-4-methoxybenzeneacetamide
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An improved method for preparing a compound having the formula STR1 which is an intermediate in the preparation of dextromethorphan, the improved method comprises the steps of (A) hydrogenating a compound having the formula STR2 in the presence of a hydrogenation catalyst to obtain a compound having the formula STR3 (B) hydrogenating the product of Step (A) in the presence of a hydrogen treated rhodium catalyst to obtain a compound having the formula STR4 (C) reacting the product of Step (B) with 4-methoxyphenylacetic acid to obtain a mixture of compounds comprising STR5 (D) dehydrating the product mixture of Step (C).
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- Interphenylene 9-thia-11-oxo-12-aza-prostanoic acids
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This invention relates to novel interphenylene 9-thia-11-oxo-12-azaprostanoic acid compounds, salts, and derivatives thereof. These compounds are exceptionally potent renal vasodilators and antihypertensives which are active when administered orally but which have a more specific type of biological activity than that of many of the natural prostaglandins and their synthetic analogs or derivatives.
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- Novel analogs of prostaglandins with 4-oxo-thiazolidinyl nucleus and method of preparation thereof
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This invention relates to novel 9-thia-, 9-oxothia-, and 9-dioxothia-11-oxo-12-azaprostanoic acid compounds, salts, and derivatives thereof and also to processes for the preparation of such compounds. These compounds have prostaglandin-like biological activity and are particularly useful as renal vasodilators, as platelet aggregation inhibitors, and for the treatment of certain autoimmune diseases.
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