- Alkyl phosphines promoted reductive coupling of acyl cyanides: formation of O-acyl cyanohydrins
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The reductive coupling of acyl cyanides promoted by alkyl phosphines has been discovered. Under mild reaction conditions, the substituted cyanohydrins were obtained in moderate to high yields by using trimethylphosphine or tributylphosphine as a promoter.
- Zhang, Wen,Shi, Min
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- Palladium-catalyzed C-H activation of simple arenes and cascade reaction with nitriles: access to 2,4,5-trisubstituted oxazoles
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An efficient and straightforward protocol for the assembly of the pharmaceutically and biologically valuable oxazole skeleton is achieved for the first time from readily available simple arenes and functionalized aliphatic nitriles. This transformation in
- Dai, Ling,Yu, Shuling,Shao, Yinlin,Li, Renhao,Chen, Zhongyan,Lv, Ningning,Chen, Jiuxi
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supporting information
p. 1376 - 1379
(2021/02/22)
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- Synthesis of Imidazoles and Oxazoles via a Palladium-Catalyzed Decarboxylative Addition/Cyclization Reaction Sequence of Aromatic Carboxylic Acids with Functionalized Aliphatic Nitriles
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We herein report an efficient approach for the assembly of multiply substituted imidazoles and oxazoles in a single-step manner. These transformations are based on a decarboxylation addition and annulation of readily accessible aromatic carboxylic acids a
- Dai, Ling,Yu, Shuling,Lv, Ningning,Ye, Xuanzeng,Shao, Yinlin,Chen, Zhongyan,Chen, Jiuxi
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supporting information
p. 5664 - 5668
(2021/08/01)
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- Divergent Palladium-Catalyzed Tandem Reaction of Cyanomethyl Benzoates with Arylboronic Acids: Synthesis of Oxazoles and Isocoumarins
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A palladium-catalyzed tandem reaction of cyanomethyl benzoates with arylboronic acids has been achieved. Substitution at the 2-position of cyanomethyl benzoates was found to be crucial for the selective synthesis of oxazoles and isocoumarins. Cyanomethyl
- Chen, Jiuxi,Chen, Zhongyan,Dai, Ling,Shao, Yinlin,Xiong, Wenzhang,Xu, Tong,Yu, Shuling
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supporting information
(2020/04/15)
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- Synthesis of 2,4,5-Trisubstituted Oxazoles via Pd-Catalyzed C-H Addition to Nitriles/Cyclization Sequences
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A practical and flexible intermolecular protocol for the diverse synthesis of trisubstituted oxazole derivatives via a Pd-catalyzed direct C-H addition of electronic-rich heteroarenes to O-acyl cyanohydrins bearing an α-hydrogen/cyclization sequence is described. A wide range of trisubstituted oxazoles can be prepared from readily available starting materials in good to high yields with high efficiency under redox neutral reaction conditions.
- Zhang, Di,Song, Hao,Cheng, Na,Liao, Wei-Wei
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supporting information
p. 2745 - 2749
(2019/04/30)
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- Synthesis of benzoyl cyanide through aerobic photooxidation of benzyl cyanide using carbon tetrabromide as a catalyst
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We developed a synthetic method toward benzoyl cyanide through aerobic photooxidation of benzyl cyanide in the presence of carbon tetrabromide under visible light irradiation with fluorescent lamps.
- Sugiura,Tachikawa,Nagasawa,Tada,Itoh
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p. 70883 - 70886
(2015/09/08)
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- Direct synthesis of cyanohydrin esters from aroyl chlorides using potassium hexacyanoferrate(II) as an eco-friendly cyanide source
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Abstract A direct synthetic method for cyanohydrin esters from aroyl chlorides using potassium hexacyanoferrate(II) as an eco-friendly cyanide source and tributylphosphine as a promoter is described. This protocol has advantages of no use of strong toxic cyanating agents, high yield, and simple work-up procedure.
- Li, Zheng,Zhao, Zhouxing
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p. 3147 - 3155
(2015/04/27)
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- Titanium-mediated addition of grignard reagents to acyl cyanohydrins: Aminocyclopropane versus 1,4-diketone formation
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The 1,2-dianion reactivity of the reagent generated from EtMgBr and titanium isopropoxide was illustrated when N-acyl cyanohydrins were used as substrates (>20 examples), giving both aminocyclopropane derivatives and 1,4-dicarbonyl compounds. When the reaction was performed in diethyl ether, 5-hydroxy-1,4-diketones were the main product. Under specific conditions (use of tetrahydrofuran and a bulky carboxylic moiety), the cyclopropane derivatives were obtained in good yields. The observed dichotomy may be explained by a ring-opening of the five-membered titanacycle intermediate followed by a nonselective acyl addition. The 1,2-dianion reactivity of the reagent generated from EtMgBr and Ti(OiPr)4 was illustrated when N-acyl cyanohydrins were used as substrates (>20 examples). When the reaction was performed in diethyl ether, 1,4-diketones were mainly isolated. Under certain conditions, cyclopropane derivatives were also obtained in good yields. A mechanism rationalizing this dichotomy is presented. Copyright
- Setzer, Paul,Forcher, Gwenael,Boeda, Fabien,Pearson-Long, Morwenna S. M.,Bertus, Philippe
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supporting information
p. 171 - 180
(2014/01/06)
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- Cyanative self-condensation of aromatic aldehydes promoted by VO(O iPr)3-Lewis base as a cooperative catalyst
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Self-condensation of aromatic aldehydes with trimethylsilyl cyanide proceeded by the cooperative catalytic effect of VO(OiPr)3 and a Lewis base to give the corresponding O-acylated cyanohydrins. The reaction conversion and selectivity were strongly dependent on the solvent used, the Lewis base, and the presence of oxygen. All the nine kinds of aromatic aldehydes considered herein afforded the O-acylated cyanohydrins with excellent selectivity under an O2 atmosphere.
- Kodama, Koichi,Kawamata, Hiroaki,Takahashi, Naoya,Hirose, Takuji
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p. 9440 - 9446
(2013/01/15)
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- Mechanistic studies on the enantioselective BINOLAM/titanium(IV)-catalyzed cyanobenzoylation of aldehydes: Part 1
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The enantioselective titanium(IV)-catalyzed cyanobenzoylation of aldehydes using 1:1 BINOLAM/Ti(OiPr)4 mixtures as a precatalyst gave O-aroyl cyanohydrins 4 with good enantiomeric excesses. The standard optimization set carried out on the assumption of Curtin-Hammett behavior, led to no amelioration. Extensive experimental and computational studies were carried out with the purpose of identifying the key mechanistic aspects governing enantioselectivity. HCN and isopropyl benzoate were detected in the reacting mixtures. This as well as the reaction response to the presence of an exogenous base, and the failure to react in the presence of Binol/Ti(OiPr)4 mixtures, led us to propose, not a direct but an indirect process involving an enantioselective hydrocyanation step followed by O-benzoylation. Computational work carried out with mononuclear monomeric MM and dinuclear mixed dimer DlMD as catalysts support this mechanistic proposal. On the other hand, cyanobenzoylations carried out with 1:2 or higher 1:n (up to 1:5) BINOLAM/Ti(OiPr)4 mixtures appear to involve a reversal of the enantioselection. This, together with the fact that the benzoylation of the ligated iPrOH is a slow reaction, has led us to conclude that these cyanobenzoylations do not fit within the standard Curtin-Hammett kinetic scheme. Instead, such BINOLAM/Ti(OiPr)4 -catalyzed cyanobenzoylations of aldehydes rather behave as non-Curtin-Hammett kinetic schemes. Further computational analysis is needed in order to make a clear distinction between Curtin-Hammett and non-Curtin-Hammett kinetic frameworks.
- Baeza, Alejandro,Najera, Carmen,Sansano, Jose M.,Saa, Jose M.
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scheme or table
p. 1282 - 1291
(2011/11/28)
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- One-Pot Three-Component Solvent-Free Cyanoaroylation of Aldehydes Using Potassium Hexacyanoferrate(II) as an Environmentally Benign Cyanide Source
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An efficient method for one-pot three-component solvent-free cyanoaroylation of aldehydes using potassium hexacyanoferrate(II) as an environmentally benign cyanide source and triethylamine as a catalyst has been described. This method has advantages of not using strongly toxic cyanating agents and volatile organic solvents. In addition, the product was obtained in high yield using a simple workup procedure.
- Li, Zheng,Tian, Guoqiang,Ma, Yuanhong
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supporting information; experimental part
p. 2164 - 2168
(2010/10/21)
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- One-pot three components synthesis of O-acetylcyanohydrins with TMSCN, acetic anhydride and carbonyl compounds under solvent-free condition
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One-pot three components synthesis of O-acetylcyanohydrins has been developed in the presence of B(C6F5)3 as the catalyst. Variety of aldehydes or ketones reacts with TMSCN and acetic anhydride (Ac2O) under the
- Kadam, Santosh T.,Kim, Sung Soo
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experimental part
p. 6330 - 6334
(2010/01/06)
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- The benzil rearrangement reaction: Trapping of a hitherto minor product and its application to the development of a selective cyanide anion indicator
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The isolation and characterization of an intermediate from the benzil-cyanide reaction is reported. The use of this trapping chemistry to produce a chemical indicator for the cyanide anion is described. It relies on the synthesis and reaction of a π-exten
- Sessler, Jonathan L.,Cho, Dong-Gyu
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- DMAP-organocatalyzed O-silyl-O-(or C-)-benzoyl interconversions by means of benzoyl fluoride
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A mild and efficient transprotection of alcohols from silyl ethers 1a-f to benzoates 2a-f is reported in fair to good yields (50-98%). This silyl-acyl exchange reaction proceeds readily in acetonitrile at room temperature in the presence of benzoyl fluoride and DMAP as an acyl transfer catalyst. A two-step 'one-pot' DMAP-catalyzed silylcyanation-transprotection sequence which gives the corresponding O-benzoyl cyanohydrines 2g-l in high yields (72-98%) from various benzaldehyde and ketone derivatives is also reported. This original organocatalytic acyl transfer process was also found to be effective in the O-benzoylation of trimethysilyl enolates 1m-o, providing enol esters 2m-o. Lastly, the potential of this strategy is also illustrated by a DMAP-mediated Claisen condensation between ketene silyl acetals 1p-r and benzoyl fluoride. Georg Thieme Verlag Stuttgart.
- Poisson, Thomas,Dalla, Vincent,Papamica?l, Cyril,Dupas, Georges,Marsais, Francis,Levacher, Vincent
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p. 381 - 386
(2008/01/08)
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- Benzotriazole-mediated alkoxyalkylation and acyloxyalkylation
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Reactions of readily available and stable 1-(α-alkoxyalkyl)benzotriazoles type 9a,b and 10a-d with a variety of silyl enol ethers 11 or 1,3-dicarbonyl compounds 13 give the expected ketones 12a-l (60-92%), β-keto esters 14a,b (62-67%), and malonates 14c,d
- Katritzky, Alan R.,Abdel-Fattah, Ashraf A.A.,Idzik, Krzysztof R.,El-Gendy, Bahaa El-Dien M.,Soloducho, Jadwiga
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p. 6477 - 6484
(2008/02/04)
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- An efficient and facile one-pot synthesis of cyanohydrin esters from carbonyl compounds catalyzed by iron(III) chloride
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A variety of cyanohydrin esters were readily prepared from carbonyl compounds with trimethylsilyl cyanide and acid anhydride under the influence of a catalytic amount of iron(III) chloride in a convenient one-pot procedure.
- Iwanami, Katsuyuki,Aoyagi, Masaru,Oriyama, Takeshi
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p. 7487 - 7490
(2007/10/03)
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- Solvent-free synthesis of cyanohydrin derivatives catalysed by triethylamine
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A very simple one-step environmentally friendly procedure for the synthesis of O-substituted cyanohydrins from aldehydes and ketones, in the absence of solvent, employing minimum amounts of the corresponding cyanides has been optimised. Aldehydes react more rapidly than ketones using triethylamine as catalyst offering in both cases almost quantitative yields of the corresponding O-trimethylsilyl, O-methoxycarbonyl, O-benzoyl and O-acetyl cyanohydrins. Georg Thieme Verlag Stuttgart.
- Baeza, Alejandro,Najera, Carmen,Retamosa, Ma. De Gracia,Sansano, Jose M.
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p. 2787 - 2797
(2007/10/03)
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- Reactions of 1,3-diaryl-2-chloropropane-1,3-diones with nucleophiles - Cyanide-induced retro-Claisen-Claisen condensation
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Treatment of some 1,3-diaryl-2-chloropropane-1,3-diones, acyclic chloro-substituted enaminones and β-oxo esters with nucleophiles was shown to proceed easily with the formation, at least in the first stage, of formal nucleophilic substitution products. Treatment of enaminones and β-oxo esters with azide and cyanide ions proceeds with the preservation of the skeleton, whereas chloro-substituted diaroylmethanes undergo retro-Claisen-Claisen condensation reactions in the course of the reaction with cyanide. Dibenzoylchloromethane reacts with azide and cyanide ions with fragmentation of the molecule and subsequent reassembly, resulting in benzoylated benzaldehyde cyanohydrin and a 1,3-oxathiol derivative, respectively. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
- Roshchupkina, Galina I.,Gatilov, Yury V.,Rybalova, Tatyana V.,Reznikov, Vladimir A.
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p. 1765 - 1773
(2007/10/03)
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- Cyanobenzoylation and hydrocyanation of aldehydes with benzoyl cyanide using no catalyst
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(Matrix presented) In the presence of MS 4A in DMSO, cyanobenzoylation of various aldehydes with benzoyl cyanide proceeded very smoothly to give the corresponding cyanohydrin benzoates in high to excellent yields without an acid or a base. On the other hand, reaction of aldehydes with BzCN in DMSO-H2O also occurred readily to afford the corresponding free cyanohydrins exclusively.
- Watahiki, Tsutomu,Ohba, Sayoko,Oriyama, Takeshi
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p. 2679 - 2681
(2007/10/03)
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- A convenient and improved method for the preparation of cyanohydrin esters from acyl cyanides and aldehydes
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Various kinds of cyanohydrin esters can be obtained in good to excellent yields from aldehydes by treatment with acyl cyanides in a heterogeneous mixture of aqueous potassium carbonate and acetonitrile.
- Okimoto, Mitsuhiro,Chiba, Toshiro
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p. 1188 - 1190
(2007/10/03)
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- Reductive Coupling of Benzoyl Cyanide and Carbonyl Compounds by Aqueous Ti(III) Ions. A New Convenient and Selective Access to the Less Stable Mixed Benzoins
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The reactive species formed by the Ti(III) ion reduction of benzoyl cyanide (1) adds to the C-atom of carbonyl compounds 2 under simple experimental conditions.The intermediate 1,2-diols 3 are smoothly converted, without isolation, into the less thermodynamically stable mixed benzoins 4, which are not accessible by the classical benzoin condensation.The possible mechanisms involved in the reaction are discussed.
- Clerici, Angelo,Porta, Ombretta
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p. 2889 - 2893
(2007/10/02)
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- Triazolo[4,5-d]pyrimidines. XII. Reactions of 6-benzoyl-6,7-dihydro-3-phenyl-3H-1,2,3-triazolo-[4,5-d]pyrimidines (triazolopyrimidine Reissert compounds) with acid, base, and electrophile
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In the treatment of 6-benzoyl-6,7-dihydro-3-phenyl-3H-1,2,3-triazolo[4,5-d]pyrimidine-7-car bonitrile (1, triazolopyrimidine Reissert compound) and 6-benzoyl-6,7-dihydro-5-methyl-3-phenyl-3H-1,2,3-triazolo[4,5-d]pyrimid ine-7-carbonitrile (2,5-methyltriazolopyrimidine Reissert compound) with an acid, the ring fission of the pyrimidine ring proceeded to give the triazole derivatives (3-7). Alkaline hydrolysis of 2 and 1 gave 5-methyl-3-phenyl- (10) and 3-phenyl-3H-1,2,3-triazolo[4,5-d]pyrimidines (9), respectively. The anions, generated from 1 and 2 with sodium hydride (NaH), underwent aromatization to give the 3H-1,2,3-triazolo[4,5-d]pyrimidine-7-carbonitriles (12 and 14). Compounds 1 and 2 reacted with arylaldehydes in the presence of NaH to give corresponding 3H-1,2,3-triazolo[4,5-d]pyrimidin-7-ylmethyl benzoates (15 and 17).
- Tanji,Sato,Kanamura,Iijima,Miyashita,Higashino
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p. 513 - 517
(2007/10/02)
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- Applications of Phase-Transfer Catalysis, 55. - New Experiments towards Enantioselective Phase-Transfer Catalysis with Optically Active Crown Ethers
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Optically active crown ethers 1a - 1o, 2, 3a, b, 4a, b, 5a - 5d, 6a, b and the acyclic analogue 7 were used for three Michael-type additions, benzoin condensation, a C-alkylation, a base-catalyzed autoxidation and a hypochlorite epoxidation.Important obse
- Dehmlow, Eckehard V.,Knufinke, Volker
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p. 283 - 286
(2007/10/02)
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- DABCO-Mediated Synthesis and Biological Activity of Cyanihydrin Esters
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Cyanohydrin esters 1-31 have been prepared from α-ketonitriles and aldehydes using DABCO (1,4-diazabicyclooctane) as nucleophilic acylation catalyst.The modofied piperonal 8 was found to inhibit the formation of thromboxane synthetase.
- Hoffmann, H. M. R.,Ismail, Z. M.,Hollweg, Reiner,Zein, Abdul R.
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p. 1807 - 1810
(2007/10/02)
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- Purines. VIII. Reactions of 1-Benzoyl-1,6-dihydro-9-phenyl-9H-purine-6-carbonitrile (9-Phenylpurine Reissert Compound) with Acid, Bases, and Electrophiles
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1-Benzoyl-1,6-dihydro-9-phenyl-9H-purine-6-carbonitrile (1, 9-phenylpurine Reissert compound) was hydrolyzed in an acid medium to give the ring fission product of the pyrimidine ring (3, 4).Alkaline hydrolysis of 1 gave 9-phenyl-9H-purine (2) and benzoic acid (5).The anion of 1 generated from 1 and sodium hydride in tetrahydrofuran underwent aromatization, resulting in the formation of 9-phenyl-9H-purine-6-carbonitrile (6) together with 2.The reaction of 1 with aromatic aldehydes in the presence of sodium hydride proceeded to give the 6-purinylmethyl benzoates (8a-c), together with 2 and 9.On the other hand, the reaction of 1 with 2,4-dinitrochlorobenzene in the presence of sodium hydride failed to give the corresponding 6-arylpurine, and the aromatization product 6 was obtained.Keywords - 9H-purine; Reissert compound anion; 9H-purin-6-ylmethyl benzoate
- Tanji, Ken-ichi,Sato, Susumu,Miyashita, Akira,Oishi, Etsuo,Higashino, Takeo
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p. 187 - 189
(2007/10/02)
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- Reactions of α-Hydroxy Carbonyl Compounds with Azodicarboxylates and Triphenylphosphine: Synthesis of α-N-Hydroxy Amino Acid Derivatives
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Reaction of aliphatic α-hydroxy esters with azodicarboxylates and triphenylphosphine in the presence of either CbzNHOCH2Ph or trOCNHOCH2Ph provides a direct route to protected α-N-hydroxy amino acids.Similar reactions with aromatic α-hydroxy carbonyl compounds and derivatives result in predominate oxidation to the corresponding α-oxo carbonyl derivatives.
- Kolasa, Teodozyj,Miller, Marvin J.
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p. 4978 - 4984
(2007/10/02)
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- Studies on Pyrazolopyrimidine Derivatives. XIV. Preparation and Reactions of 1-Phenyl-1H-pyrazolo-pyrimidine Reissert Compound
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The Reissert reaction of 1-phenyl-1H-pyrazolopyrimidine (4) in anhydrous methylene chloride using benzoyl chloride, trimethylsilyl cyanide, and a catalytic amount of aluminium chloride gave the corresponding Reissert compound (3, 5-benzoyl-4,5-dihydro-1-phenyl-1H-pyrazolopyrimidine-4-carbonitrile) in 95percent yield.The alkaline hydrolysis of 3 in methanol resulted in the formation of 4, benzoic acid (7), and the 4,4'-dimer (9) of (4).The acid hydrolysis in dimethyl sulfoxide and in methanol proceeded with ring fission to give 5-amino-α-benzamido-1-phenyl-1H-pyrazole-4-acetonitrile (13), the acetamide (14), and the acetate (15).Compound 3 reacted with sodium hydride in dimethylformamide to give 4, 9, 1-phenyl-1H-pyrazolopyrimidine-4-carbonitrile (20), α,1-diphenyl-1H-pyrazolopyrimidin-4-ylmethyl benzoate (21), and O-benzoylmandelonitrile (22).In the present paper, we compare the chemical properties of 3 with those of the isoquinoline Reissert compound (1, 2-benzoyl-1,2-dihydro-1-isoquinolinecarbonitrile).Keywords-pyrazolopyrimidine Reissert compound; preparation; chemical property; hydrolysis; pyrazoleacetonitrile; carbanion; rearrangement; pyrazolopyrimidinemethanol
- Higashino, Takeo,Sato, Susumu,Miyashita, Akira,Katori, Tatsuhiko
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p. 4569 - 4576
(2007/10/02)
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- A Simple One-Pot Synthesis of Silylated and Acylated Cyanohydrins
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Reaction of variety of aldehydes and ketones with chlorotrimethylsilane and acyl chlorides in the presence of lithium cyanide to give trimethylsilylcyanohydrins and acylcyanohydrins is described.
- Yoneda, Ryuji,Santo, Kazunori,Harusawa, Shinya,Kurihara, Takushi
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p. 1054 - 1055
(2007/10/02)
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- CYANOHYDRINS AS SUBSTRATES IN BENZOIN CONDENSATION. REGIOCONTROLLED MIXED BENZOIN CONDENSATION
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O-Benzoylated cyanohydrins of aromatic aldehydes have been used as one of the substrates in the benzoin condensation.They were treated with aromatic aldehydes under phase-transfer conditions to result in benzoin benzoates.By this method aldehydes which fail to undergo condensation using traditional conditions could be converted into benzoins.By the Umpolung of reactivity of the pertinent aldehyde it was possible to prepare both isomeric unsymmetrical benzoins, including the thermodynamically less stable ones.
- Rozwadowska, Maria D.
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p. 3135 - 3140
(2007/10/02)
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- CROWN ETHER CATALYSIS IN THE SYNTHESIS OF CYANOHYDRIN DERIVATIVES
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Carbonyl compounds react with cyanide ion under phase transfer catalysis (18-crown-6) to give cyanohydrin anions which are trapped by acid chlorides, anhydrides or alkylating agents to give cyanohydrin derivatives.
- Chenevert, Robert,Plante, Raymond,Voyer, Normand
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p. 403 - 410
(2007/10/02)
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- Studies on Pyrazolopyrimidine Derivatives. XIII. Aryl Migration of 4-Aroyl-1H-pyrazolopyrimidines to 4-Aryl-4,5-dihydro-1H-pyrazolopyrimidine-4-carboxylic Acids
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When a mixture of 4-aroyl-1-phenyl-1H-pyrazolopyrimidines (3) and sodium hydroxide in dimethyl sulfoxide (DMSO) was stirred for 1 h at room temperature, migration of the aryl group to the 4-position occurred, i.e., the benzilic acid rearrangement,
- Higashino, Takeo,Matsushita, Yasuhiko,Takemoto, Masumi,Hayashi, Eisaku
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p. 3951 - 3958
(2007/10/02)
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- Process for preparing cyanohydrin esters
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Cyanohydrin esters are prepared by reacting a carboxylic acid anhydride represented by the formula STR1 with an alkali metal cyanide and an alkali metal borohydride.
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