6047-90-1Relevant academic research and scientific papers
α,β-Unsaturated acyl cyanide synthesis via triethylamine catalyzed redox cyanation
Choi, Hyung Ho,Son, Young Hoon,Jung, Min Seok,Kang, Eun Joo
supporting information; experimental part, p. 2312 - 2315 (2011/05/09)
Stereoselective redox cyanation of alkynyl aldehydes was explored, furnishing (E)-α,β-unsaturated acyl cyanides. This reaction was catalyzed by mild TEA base, as a dual role of Lewis base and Bro?nsted base. TMSCN treated with TEA was an effective reagent for generating umpolung intermediates from alkynyl aldehydes, and this nucleophilic intermediate can be protonated by equimolar amount of EtOH, promoting the efficient conversion into α,β-unsaturated acyl cyanides. The synthesized acyl cyanides were successfully applied as the synthetic precursors in the iron-catalyzed arylation reactions.
Dibutyltin dimethoxide-catalyzed cyano transfer to aldehydes and imines
Yanagisawa, Akira,Matsumoto, Takuya,Kushihara, Naoyuki,Yoshida, Kazuhiro
experimental part, p. 2918 - 2922 (2011/01/05)
A novel reaction involving cyano transfer from benzophenone cyanohydrin to aldehydes and imines was realized by using dibutyltin dimethoxide as a catalyst. Various cyanohydrins and α-amino nitriles were obtained in moderate to high yields by this reaction. Ketimines also showed remarkable reactivity as cyano acceptors under conventional reaction conditions. This catalytic reaction was further applied to a three-component condensation reaction of aldehydes, aniline, and benzophenone cyanohydrin in the presence of Drierite. Copyright
Lewis acid-lewis base-catalysed enantioselective addition of α-ketonitriles to aldehydes
Lundgren, Stina,Wingstrand, Erica,Moberg, Christina
, p. 364 - 372 (2008/02/07)
Additions of structurally diverse α-ketonitriles to aromatic and aliphatic prochiral aldehydes yielding highly enantioenriched acylated cyanohydrins were achieved using a combination of a titanium salen dimer and an achiral or chiral Lewis base. In most cases high yields and high enantioselectivities were observed. The ee was moderate in the initial part of the reaction but increased over time. This could be avoided, and higher ees obtained, by keeping the titanium complex, in the presence or absence of aldehyde and ketonitrile, at -40°C prior to the addition of the Lewis base. A mechanism initiated by nucleophilic attack of the tertiary amine at the carbonyl carbon atom of the ketonitile is supported by 13C labelling experiments.
Synthesis and nitrosation reactions of π-extended 1,3-dithiol-2- ylidene systems
Bryce, Martin R.,Chalton, Michael A.,Chesney, Antony,Catterick, David,Yao, Jing W.,Howard, Judith A.K.
, p. 3919 - 3928 (2007/10/03)
New 1,3-dithiol-2-ylidene derivatives, notably π-extended systems, have been synthesised by Wittig reactions of phosphorane and phosphonate ester derivatives of 1,3-dithiole with activated ketones and α,β-unsaturated ketones. Nitrosation reactions of a range of these π-extended systems, results in the formation of nitroalkenes, via unstable nitrosoalkene intermediates, which, in general, could not be isolated. The X-ray crystal structure of 1-(4,5-dicarbomethoxy-1,3-dithiol-2-ylidene)-1-cyano-1-phenyl- methane reveals a small degree of intramolecular electron transfer from the dithiole ring to the conjugated cyano group.
Ruthenium-Catalyzed Oxidations of Alcohols
Murahashi,Naota
, p. 203 - 213 (2007/10/03)
A combination of low-valent ruthenium complexes and peroxides such as t-BuOOH and peracids serves as efficient catalytic systems for the oxidation of aromatic and aliphatic hydroxy compounds. The utility of these methods was demonstrated by the synthesis of acyl cyanides which are versatile synthetic intermediates. The principle of the catalytic oxidations with peracids lead to the novel and efficient method for aerobic oxidation of alcohols in the presence of aldehydes. This reaction is of importance in synthetic and large scale industrial processes and from environmental points of view. The present principle will provide new chemistry of oxidative transformations of various industrially important functional materials.
Ruthenium-catalyzed oxidations for selective syntheses of ketones and acyl cyanides. Selective acylation of amino compounds with acyl cyanides
Murahashi,Naota
, p. 433 - 440 (2007/10/02)
Oxidation of alcohols to the corresponding carbonyl compounds with tert-butyl hydroperoxide in the presence of dichlorotris(triphenylphosphine)ruthenium catalyst gives the corresponding carbonyl compounds with high efficiency. This method can be applied to the oxidation of cyanohydrins to give acyl cyanides which are versatile synthetic intermediates. Acylation of amino compounds with acyl cyanides thus obtained proceeds chemoselectively. Thus, the reaction of amino alcohols with acyl cynides gives N-acylated products exclusively. In the similar N-acylation of polyamines primary amines are selectively acylated in the presence of secondary amines. These reactions are highly useful for the synthesis of spermidine and spermine alkaloids such as spermidine alkaloids such as spermidine siderophores. Dimeric cyclocoupling reaction of diacyl cyanides such as iso- and terephthaloyl cyanides with polyamines can be performed under the similar reaction conditions to give the corresponding polyazamacrocycles with high efficiency.
Chemoselective Acylation of Primary Amines in the Presence of Secondary Amines with Acyl Cyanides. Highly Efficient Methods for the Synthesis of Spermidine and Spermine Alkaloid
Murahashi, Shun-Ichi,Naota, Takeshi,Nakajima, Nobuyuki
, p. 879 - 882 (2007/10/02)
Acyl cyanides are highly useful reagents for the chemoselective acylation of primary amines in the presence of secondary amines.The reaction provides the versatile method for the shortstep synthesis of various naturally occurring polyamines.
Reaction of Aromatic Acyl Chlorides with Potassium or Sodium Cyanide Impregnated onto Amberlite XAD Resins. Efficient Synthesis of Aromatic Acyl Cyanides
Sukata, Kazuaki
, p. 1085 - 1090 (2007/10/02)
The effects of alkali metal cyanide impregnated on Amberlite XAD resins (KCN/XAD, NaCN/XAD) have been examined using the cyanation of benzoyl chloride.In benzene, benzoyl cyanide was obtained in a very high yield with high selectivity under mild conditions.It is proposed that the reaction occurs on the surface of the resin.On the basis of the result obtained in the absence of any solvent, the reactivity of KCN/XAD toward dimerization of benzoyl cyanide has been found to be much poorer than that of KCN in solution.Although the reaction of acyl chlorides with KCN/XADor NaCN/XAD in benzene gave various acyl cyanides in good to excellent yields, no aliphatic acyl cyanide could be obtained.
α,β-Unsaturated Acyl Cyanides. 6. Self-Condensation and Conjugate Addition of Allyl, Allenyl-, Propargyl-, and Alkynyltrimethylsilanes
Santelli, Maurice,Abed, Douniazad El,Jellal, Abdelkebir
, p. 1199 - 1206 (2007/10/02)
The base-induced reaction of α,β-unsaturated acyl cyanides leads to lactones resulting from a self condensation reaction.Neutral nucleophiles such as trimethylsilyl derivatives react with α,β-unsaturated acyl cyanides in the presence of titanium tetrachloride. δ-Ethylenic acyl cyanides, δ-acetylenic acyl cyanides, γ-allenic acyl cyanides, and γ-acetylenic acyl cyanides (or the corresponding acids or methyl esters) are obtained from α,β-unsaturated acyl cyanides by condensation respectively with allyl-, allenyl-, propargyl- and alkynyltrimethylsilanes.
RUTHENIUM CATALYZED OXIDATION OF CYANOHYDRINS TO ACYL CYANIDES USEFUL REAGENTS FOR SELECTIVE N-BENZOYLATION OF AMINOALCOHOLS
Murahashi, Shun-ichi,Naota, Takeshi,Nakajima, Nobuyuki
, p. 925 - 928 (2007/10/02)
Ruthenium catalyzed oxidation of cyanohydrins with tert-butyl hydroperoxide gives the corresponding acyl cyanides in good to excellent yields.Acyl cyanides thus obtained are useful reagents for selective N-benzoylation of aminoalcohols.
