Solvent‐free cyanosilylation of ketones with (CH3)3SiCN (TMSCN) catalyzed by NbF5

The addition of TMSCN to ketones catalyzed by dispersed NbF₅ gave corresponding cyanohydrin trimethylsilylethers with excellent yield (>90%). Cyano transfer occurs within 30 min at room temperature in the presence of 1 mol% of NbF₅ under solvent‐free conditions. These conditions are extremely mild, simple, and tolerate various functional groups. Copyright © 2007 John Wiley & Sons, Ltd.     

Zr(HSO4)4 catalyzed one-pot strecker synthesis of α-amino nitriles from aldehydes and ketones under solvent-free conditions

A mild and efficient method has been developed for the preparation of α-amino nitriles from the condensation of aldehydes and ketones with aniline and TMSCN in the presence of a catalytic amount of Zr(HSO₄)₄ under solvent-free conditions at room temperature.     

Synthesis of α-aminonitriles under mild catalytic,metal-free conditions

α-Aminonitriles have been synthesized by a Strecker synthesis from aldehydes and ketones under mild catalytic, metal-free conditions. Aromatic aldehydes (1 equiv) were reacted with aromatic and 1° or 2° aliphatic amines (1 equiv) in EtOH containing 3 mol % of NH₄Cl to give high yields of α-aminonitriles. An alternative to adding NH₄Cl as a catalyst involved the use of excess TMSCN (1 equiv) and to promote the process. The reaction was also successful under microwave conditions using excess TMSCN with no solvent. Ketones similarly reacted with aromatic amines and excess TMSCN under conventional and microwave heating, but 30 mol % of added NH₄Cl was required for optimum conversion.     

Fe(Cp)2PF6: An efficient catalyst for cyanosilylation of carbonyl compounds under solvent free condition

An efficient method for the addition of trimethylsilyl cyanide (TMSCN) to various aldehydes and ketones has been described using Fe(Cp)₂PF₆ (2.5 mol%) as a catalyst under solvent free condition. Excellent yields of trimethylsilylether of cyanohydrin up to (94%) was achieved within 10 min.     

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.     

Highly efficient and convenient Strecker reaction of carbonyl compounds and amines with TMSCN catalyzed by MCM-41 anchored sulfonic acid as a recoverable catalyst

MCM-41 anchored sulfonic acid (MCM-41–SO₃H) was found to be a highly efficient and recoverable heterogeneous catalyst for the three-component Strecker reaction of aldehydes or ketones and diverse amines using trimethylsilyl cyanide (TMSCN) to afford the corresponding α-amino nitriles under mild conditions in high to quantitative yields. The simple experimental procedure along with easy recovery and reusability of the catalyst has led to development of a clean and environmentally friendly approach for the synthesis of α-amino nitriles.     

Enantioselective cyanosilylation of ketones catalyzed by Mn(salen)/Ph3PO

TMSCN asymmetrically adds to a variety of ketones by catalysis with 1/Ph₃PO. This is a double activation where 1 acts as a Lewis acid and Ph₃PO as a Lewis base. Various ketones were subjected to the enantioselective addition to give up to 85% ee.     

Highly Efficient Cyanosilylation of Aldehydes and Ketones under Microwave,Solvent‐Free,and Lewis Acid–Free Conditions

The addition of TMSCN to aldehydes and ketones under microwave irradiation in the absence of any Lewis or Brønsted acid and solvent yielded the corresponding cyanohydrins in good yields in short reaction times (less than 30 min).     

Green Biginelli‐type Reaction: Solvent‐free Synthesis of 5‐unsubstituted 3,4‐dihydropyrimdin‐2(1H)‐ones

The Biginelli‐type compounds, 5‐unsubstituted 3,4‐dihydropyrimdin‐2(1H)‐ones were synthesized by a one‐pot three‐component condensation of aromatic aldehydes, aromatic ketones and urea in the presence of SnCl₄ · 5H₂O under solvent‐free conditions. The advantages of this method are short reaction time (4–10 min), excellent yields (74–97%), inexpensive catalyst and solvent‐free conditions. A plausible mechanism was proposed.     

Poly(diallyldimethylammonium chloride) as an Efficient Phase Transfer Catalyst in Solvent‐Free Reduction of Carbonyl Compounds with NaBH4

Poly(diallyldimethylammonium chloride) resin was used as an efficient polymeric phase transfer catalyst, which catalyzed the chemoselective reduction of aldehydes and ketones by NaBH₄ to give the corresponding alcohols in high yields under solvent-free conditions.     

Fe3O4@SiO2‐imid‐PMAn Magnetic Porous Nanosphere as Reusable Catalyst for Synthesis of Polysubstituted Quinolines under Solvent‐free Conditions

In this research, a facile one‐pot synthesis of poly‐substituted quinoline derivatives has been demonstrated by using 2‐aminobenzophenones and ethylacetoacetate or ketones in the presence of Fe₃O₄@SiO₂‐imid‐PMAⁿ and Fe₃O₄@SiO₂‐imid‐PMA^b nanoparticles as green and reusable catalysts under solvent‐free conditions. The reaction proceeds efficiently in excellent yields and in a state of excellent purity. The nanocatalysts can be recycled and reused for at least four times without noticeably decreasing in catalytic activity.     

Internally Reuse Waste: Catalytic Asymmetric One‐Pot Strecker Reaction of Fluoroalkyl Ketones,Anilines and TMSCN by Sequential Catalysis

We report a highly enantioselective one‐pot facile synthesis of fluorinated C^α‐tetrasubstituted amino nitriles from α‐fluoroalkyl α‐aryl ketones, anilines, and TMSCN through a sequential p‐TsOH catalyzed ketimine formation and chiral bifunctional tertiary amine mediated asymmetric Strecker reaction. This one‐pot approach has two important advantages. First, it greatly improves the overall yield of the synthesis of chiral C^α‐tetrasubstituted fluorinated aminonitriles from ketones, because the purification of α‐fluorinated ketimines by column chromatography suffers from great yield loss. Second, it represents the first example of asymmetric tandem reactions that can simultaneously reuse the by‐product and catalyst from the upstream step as a promoter and an additive to improve the reactivity and enantioselectivity of the subsequent catalytic enantioselective reaction, respectively. It could utilize the by‐product H₂O generated in‐situ from the ketimine formation step to activate TMSCN to form HCN, and concurrently reuse the remaining p‐TsOH acid as an additive to improve enantioselectivity.     

Ruthenium Trichloride Catalyzed Highly Efficient Deoximation of Oximes to the Carbonyl Compounds and Nitriles without Acceptors

An acceptor‐free catalysis protocol for the deoximation of ketoximes and aldoximes using RuCl₃ as the catalyst has been developed. Under the optimized conditions, various oximes were converted to ketones and nitriles with excellent isolated yields.     

Aldol Condensations Catalyzed by PEG400 and Anhydrous K2CO3 Without Solvent

Abstract

Aldol condensations of aromatic aldehydes with ketones under solvent‐free conditions to synthesize α,β‐unsaturated ketones in good to excellent yields using PEG400 and powdered anhydrous K₂CO₃ as catalysts at 90 °C and 120 °C are described.     

L-Proline Catalyzed Enamination of β-Dicarbonyl Compounds under Solvent-free Conditions

A simple, general and efficient method has been developed for synthesis of various β-enamino ketones and esters by reacting β-dicarbonyl compounds with amines using a catalytic amount of L-proline at room temperature under solvent-free conditions in excellent yields.     

An efficient hydrocyanation of α, β-unsaturated diesters with TMSCN catalyzed by MgI2 etherate

Abstract

A mild, efficient and highly regioselective addition of trimethylsilyl cyanide (TMSCN) to α,β-unsaturated diesters has been achieved by using MgI₂ etherate as catalyst under solvent-free conditions. This protocol provides the corresponding β-cyano esters in high yields.     

Cyanosilylation of Aldehydes and Ketones Catalyzed by Nanocrystalline Magnesium Oxide

Abstract

Cyanosilylation of various aldehydes and ketones with TMSCN proceeded smoothly under mild conditions to give the corresponding cyanohydrin trimethylsilyl ethers in the presence of nanocrystalline magnesium oxide. The cyanohydrin trimethylsilyl ethers of aldehydes produced cyanohydrins in good to high yields on treatment with 2 N HCl. ²⁹Si NMR spectral evidence proved that the reaction proceeds through the hypervalent silicate species by coordination to O^2?/O^? (Lewis basic site) of nanocrystalline magnesium oxide.     

An efficient conjugate hydrocyanation of chalcones and related enones with TMSCN under solvent- and additive-free microwave conditions

A first example of solvent- and additive-free 1,4-addition reaction of α,β-unsaturated ketones such as chalcones, 3-nonen-2-one and benzalacetone with trimethylsilyl cyanide (TMSCN) is described. The addition of TMSCN to chalcones, 3-nonen-2-one, and benzalacetone under microwave irradiation in the absence of Lewis or Brønsted acids and solvents, yielded the corresponding β-cyanoketones in good to moderate yields, as quite rapidly as in 5 min. No systematic substituent effect of chalcones on the yields was observed. No reaction of α,β-unsaturated esters such as methyl cinnamate with TMSCN took place under the same conditions.     

Dodecatungestophosphoric acid (H3PW12O40) as a solid green BrØnsted acid catalyzes high yielding and efficient trimethylcyanosylilation reactions of aldehydes and ketones by trimethylsilyl cyanide

An efficient solvent-free method is described for the addition of TMSCN to carbonyl groups employing dodecatungestophosphoric acid (H₃PW₁₂O₄₀) as a heterogeneous and environmentally benign catalyst. By this method, aromatic, aliphatic, cyclic and heterocyclic aldehydes and ketones are converted into their corresponding cyanotrimethylsilyl ethers in excellent yields (89-98%) in short reaction times (<10 min).     

PPA-SiO_2 as a Heterogeneous Catalyst for Efficient Synthesis of 2-Substituted-1,2,3,4-tetrahydro-4-quinazolinones under Solvent-free Conditions

Silica‐supported polyphosphoric acid (PPA‐SiO₂) catalyzed efficiently the reaction of anthranilamide with aryl aldehydes or ketones under solvent‐free conditions to afford the corresponding 1,2,3,4‐tetrahydro‐4‐quinazolinone derivatives. This work consistently has the advantages of excellent yields, short reaction time, simple experimental and work‐up procedures. The heterogeneous catalyst could be recovered and recycled for several times without any loss of its activity.