Convenient and rapid synthesis of α-aminonitriles starting directly from nitro compounds in water

A distinct approach for the synthesis of α-aminonitriles has been discovered by three-component reaction of nitroarenes, aldehydes, and TMSCN using indium in dilute aqueous HCl at room temperature. The products were formed in high yields (86-96%) within a short period of time (5-20 min). This one-pot conversion consists of the following steps: (i) reduction of nitro compounds to amines, (ii) formation of imines from amines and aldehydes and (iii) addition of cyanide anion to the imines.     

Me2(CH2Cl)SiCN和Me3SiCN在醛的不对称氰化反应中的比较研究

研究考察了在手性（salen）AlCl-叶立德络合物（R,R）-1/2a作为催化剂和异丙醚作为溶剂的条件下,两种不同硅氰化试剂[Me₂（CH₂Cl）SiCN和Me₃SiCN（TMSCN）]在对醛的不对称氰化中的应用情况.一系列不同取代的芳香醛均可分别与这两种试剂发生反应,以高到优秀的产率和对映选择性得到目标产物.脂肪醛的反应产物的对映选择性最高只能达到中等.对比研究发现,Me₂（CH₂Cl）SiCN在醛的硅氰化反应中显示出了明显高于TMSCN的反应活性,但是产物的对映选择性大体相当.     

Ionic liquid [omim][PF6] as an efficient and recyclable reaction media for the cyanosilylation of aldehydes without Lewis acid or any special activation

Ionic liquid [omim][PF₆] has been demonstrated as an efficient and environmentally friendly reaction media as well as a promoter for the cyanosilylation of aldehydes under mild conditions. In addition, the recovered ionic liquid could be reused for subsequent runs with only a gradual decrease in activity.     

Mild and efficient silylcyanation of ketones catalyzed by cesium fluoride

An efficient method of addition of trimethylsilylcyanide to ketones by employing cesium fluoride as catalyst has been described. A variety of aromatic, aliphatic, cyclic and heterocyclic ketones have been converted into their corresponding trimethylsilyl ethers in excellent yield.     

Trimethylsilyl cyanide addition to aldimines and its application in the synthesis of (S)-phenylglycine methyl ester

The addition of TMSCN to a variety of arylaldimines (Strecker reaction) in the presence of LiClO₄ or BF₃·Et₂O in acetonitrile has been studied. The reaction provided the addition products in very high yields. The method has been successfully utilized for the synthesis of (S)-phenylglycine methyl ester.     

Computational study on 1,1,3,3-tetramethylguanidine-catalyzed cyanosilylation mechanism of hypnone

The reaction mechanism of cyanosilylation of hypnone catalyzed by 1,1,3,3-tetramethylguanidine (TMG) was investigated using the density functional theory at the Becke three-parameter hybrid functional combined with Lee–Yang–Parr correlation functional (B3LYP)/6-31G(d), B3LYP/6-31G(d, p) and B3LYP/6-311++G(d, p) levels. The results show that the title reaction occurs through two processes, the formation of the intermediate five through the interaction of TMG with trimethylsilyl cyanide (TMSCN) and the reaction between the intermediate five and hypnone. The formation of intermediate five controls the whole reaction with a Gibbs free energy barrier of 31.84 kcal/mol. In addition, the results indicate that the catalyst TMG significantly promotes the title reaction and changes the mechanism. The results are in reasonable agreement with the experimental observations. Our results reveal that the overall reaction is stepwise and exoergonic in solvent-free conditions at room temperature.     

Highly active bifunctional salenTi(Ⅳ) catalysts for asymmetric cyanosilylation of aldehydes and TMSCN

A novel enantiopure salen ligand bearing a diphenylphosphine oxide on the 3-position of one aromatic ring was synthesized and combined with Ti(Oi-Pr)_4 as a monometallic bifunctional catalyst for asymmetric cyanosilylation reaction of aldehydes with tnmethylsilyl cyanide(TMSCN).The catalyst system exhibited excellent activity and moderate enantioselectivity.The addition of TMSCN to 4-nitrobenzaldehyde in the presence of 1 mol%catalyst loading could complete within 10 min at ambient temperature. An intram...     

One-pot three components synthesis of O-acetylcyanohydrins with TMSCN, acetic anhydride and carbonyl compounds under solvent-free condition

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 influence of 1 mol % of B(C₆F₅)₃ to give good to excellent yield of the products without solvent at rt.     

Ionic liquid-promoted one-pot oxidative Michael addition of TMSCN to Baylis-Hillman adducts

The first example of ionic liquid-promoted one-pot oxidative conjugate hydrocyanation of Baylis-Hillman adducts with trimethylsilyl cyanide (TMSCN) is reported. The oxidation of Baylis-Hillman adducts with IBX/[bmim]Br or isomerization-oxidation with NaNO₃/[Hmim]HSO₄ systems affords β-ketomethylene compounds or [E]-cinnamaldehydes, respectively. These α,β-unsaturated carbonyl compounds undergo Michael addition with TMSCN in the same vessel to afford the corresponding thermodynamically more stable β-cyanated products. Thermodynamically less stable 1,2-addition products were not formed. The present regioselective reactions are promoted by ionic liquids, which can be recycled easily for further use without any loss of efficiency.