- Ni-Catalyzed Isomerization-Hydrocyanation Tandem Reactions: Access to Linear Nitriles from Aliphatic Internal Olefins
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A highly regioselective nickel-based catalyst system for the isomerization/hydrocyanation of aliphatic internal olefins is described. This benign tandem reaction provides facile access to a wide variety of aliphatic nitriles in good yields with excellent regioselectivities. Thanks to Lewis acid-free conditions, the protocol features board functional groups tolerance, including secondary amine and unprotected alcohol groups.
- Gao, Jihui,Ni, Jie,Yu, Rongrong,Cheng, Gui-Juan,Fang, Xianjie
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supporting information
p. 486 - 490
(2021/02/05)
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- Process for the Catalytic Reversible Alkene-Nitrile Interconversion
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The present invention refers to processes for catalytic reversible alkene-nitrile interconversion through controllable HCN-free transfer hydrocyanation.
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Page/Page column 23; 24
(2017/09/02)
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- Radical cyanation of alkyl iodides with diethylphosphoryl cyanide
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The β-elimination of an organophosphoryl group from an iminyl radical is observed for the first time. On the basis of this finding, radical cyanation of alkyl iodides is achieved by using diethylphosphoryl cyanide. Georg Thieme Verlag Stuttgart.
- Chang, Ho Cho,Jin, Young Lee,Kim, Sunggak
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experimental part
p. 81 - 84
(2009/05/30)
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- A simple one-pot procedure for the direct conversion of alcohols into alkyl nitriles using TsIm
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A convenient and efficient one-pot preparation of nitriles from alcohols using N-(p-toluenesulfonyl)imidazole (TsIm) is described. In this method, treatment of alcohols with a mixture of NaCN, TsIm and triethylamine in the presence of catalytic amounts of tetra-n-butylammonium iodide (TBAI) in refluxing DMF furnishes the corresponding alkyl nitriles in good yields. This methodology is highly efficient for various structurally diverse alcohols with selectivity for ROH: 1° > 2° > 3°.
- Soltani Rad, Mohammad Navid,Khalafi-Nezhad, Ali,Behrouz, Somayeh,Faghihi, Mohammad Ali
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p. 6779 - 6784
(2008/02/13)
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- Radical cyanocarbonylation using alkyl allyl sulfone precursors
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Acyl cyanides have been prepared by the three-component coupling reactions comprised of alkyl allyl sulfones, carbon monoxide, and p-tolylsulfonyl cyanide under tin-free radical reaction conditions. Georg Thieme Verlag Stuttgart.
- Kim, Sangmo,Cho, Chang Ho,Kim, Sunggak,Uenoyama, Yoshitaka,Ryu, Ilhyong
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p. 3160 - 3162
(2007/10/03)
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- Efficient conversion of tetrahydropyranyl (THP) ethers to their corresponding cyanides with triphenylphosphine/2,3-dichloro-5,6- dicyanobenzoquinone/n-Bu4 NCN
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Tetrahydropyranyl ethers were converted to their corresponding alkyl cyanides efficiently by using the triphenylphosphine/ 2,3-dichloro-5,6- dicyanobenoquinone / n-Bu4 NCN system in refluxing acetonitrile with good-to-excellent yields.
- Akhlaghinia, Batool
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p. 1783 - 1786
(2007/10/03)
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- Conversion of Alcohols, Thiols, and Trimethysilyl Ethers to Alkyl Cyanides Using Triphenylphosphine/2,3-Dichlorol-5,6-dicyanobenzoquinone/n-Bu 4NCN
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Triphenylphosphine and 2,3-dichloro-5,6-dicyanobenzoquinone afford an adduct, which in the presence of n-Bu4NCN converts alcohols, thiols, and trimethylsilyl ethers into their corresponding alkyl cyanides in good to excellent yields at room tem
- Iranpoor, Nasser,Firouzabadi, Habib,Akhlaghinia, Batool,Nowrouzi, Najmeh
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p. 2562 - 2564
(2007/10/03)
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- Tin-free radical cyanation of alkyl iodides and alkyl phenyl tellurides
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As a result of much faster phenyl telluride group transfer relative to the corresponding iodine atom transfer, tin-free radical cyanation of alkyl phenyl tellurides has been achieved with p-toluenesufonyl cyanide and methyl allyl sulfone in the presence of V-40 as initiator.
- Kim, Sunggak,Song, Hyun-Ji
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p. 2110 - 2112
(2007/10/03)
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- Azide and Cyanide Displacements via Hypervalent Silicate Intermediates
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Hypervalent azido- and cyanosilicate derivatives, prepared in situ by the reaction of trimethylsilyl azide or trimethylsilyl cyanide, respectively, with tetrabutylammonium fluoride, are effective sources of nucleophilic azide or cyanide. Primary and secondary alkyl halides and sulfonates undergo rapid and efficient azide or cyanide displacement in the absence of phase transfer catalysts with the silicate derivatives. Application of these reagents to the stereoselective synthesis of glycosyl azide derivatives is reported.
- Soli, Eric D.,Manoso, Amy S.,Patterson, Michael C.,DeShong, Philip,Favor, David A.,Hirschmann, Ralph,Smith III, Amos B.
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p. 3171 - 3177
(2007/10/03)
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- A convenient preparation of alkyl nitriles by the Mitsunobu procedure
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A convenient preparation of alkyl nitriles from alcohols extending the use of the Mitsunobu reaction is described. Acetone cyanohydrin is the acidic component and the source of cyanide ion.
- Wilk
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p. 2481 - 2484
(2007/10/02)
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- The Isonitrile-Nitrile Rearrangement. A Reaction without a Structure-Reactivity Relationship
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Reproducible rates of isomerisation of aliphatic isonitriles to nitriles in solution can be measured by GLC or IR when free-radical inhibitors are added to suppress a competing radical chain reaction.The reactivities of 19 primary, secondary, tertiary, cyclic, bicyclic, bridgehead, benzyl, substituted-benzyl, α-carbomethoxymethyl, and triphenylmethyl isocyanides in this rearrangement reaction vary by only a factor of 67 in rate or by +/- 2 kcal mol-1 in ΔG(excit.).This is explained by a tight hypervalent three-membered cyclic transition state in agreement with a previous prediction by ab initio calculation.The slower rate of 9-triptycyl isocyanide is proposed to be due to steric hindrance by the three peri hydrogens.Aromatic isocyanides isomerize about 10 times faster independent of polar para substituents and bulky ortho substituents.A hypervalent orthogonal transition state with retention of the aromatic sextet is proposed in contrast to the popular phenonium-type transition states for aryl migration in other 1,2-rearrangements.The reactivity data and the transition-state structures are discussed in context with other cationotropic 1,2-shifts.
- Meier, Michael,Mueller, Barbara,Ruechardt, Christoph
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p. 648 - 652
(2007/10/02)
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- Ameliorations et simplifications de la synthese de nitriles par alkylation de l'anion cyanure: catalyse par transfert de phase solide-liquide sans solvant
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Alkyl cyanides are obtained in very good yields and under mild conditions by reacting finely ground KCN and the corresponding alkyl halides in the presence of catalytic amounts of tetraalkylammonium salt (Aliquat 336).The addition of small amount of water (1 equivalent) is necessary.
- Bram, G.,Loupy, A.,Pedoussaut, M.
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p. 124 - 128
(2007/10/02)
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- Hydrocyanation of α,ω-Diynes Catalyzed by Tetracyanonickelate. Regiospecific Synthesis of a New Series of Acyclic Dinitriles
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Hydrocyanation of α,ω-diynes without the use of HCN has been described.Cyanonickelate, prepared by reducing 2- with NaBH4 or Zn in the presence of excess KCN in water or ethylene glycol, catalyzes hydrocyanation of α,ω-diynes, HCC(CH2)nCCH to give quantitatively CH3CH(CN)(CH2)nCH(CN)CH3, a new series of acyclic dinitriles.Importance of the preliminary formation of a (?-acetylene)nickel(0) complex for the hydrocyanation has been suggested.
- Funabiki, Takuzo,Sato, Yoshihiro,Yoshida, Satohiro
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p. 2863 - 2864
(2007/10/02)
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- Oxidative Decyanation of Secondary Nitriles to Ketones
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Procedures for the oxidative decyanation of secondary nitriles to ketones involve (1) iodination of N-(trialkylsilyl)ketenimines derived from secondary nitriles and subsequent hydrolysis of the α-iodo nitriles with silver oxide, (2) addition of nitrosobenzene to N-(trialkylsilyl)ketenimines, (3) conversion of secondary nitriles to α-(phenylthio) nitriles and subsequent hydrolysis with N-bromosuccinimide in aqueous acetonitrile, and (4) preparation of α-hydroperoxy nitriles by direct oxygenation of anions of secondary nitriles and subsequent reductive hydrolysis with stannous chloride followed by sodium hydroxide.The latter general procedure was applied to various secondary nitriles bearing dialkyl, aryl and alkyl, and diaryl substituents to provide ketones in good yield and was extended to the oxidative decyanation of α,β-unsaturated nitriles to furnish α,β-unsaturated ketones.
- Freerksen, Robert W.,Selikson, Sandra J.,Wroble, Randall R.,Kyler, S. Keith,Watt, David S.
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p. 4087 - 4096
(2007/10/02)
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- Direct One-Step Conversion of Alcohols into Nitriles
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Alcohols are converted into nitriles in good to excellent yields by treatment with 2 equiv of NaCN/Me3SiCl and a catalytic amount of NaI in DMF/CH3CN.
- Davis, Roman,Untch, Karl G.
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p. 2985 - 2987
(2007/10/02)
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