63064-15-3

Upstream product

• 930-68-7 cyclohexenone 
• 140-29-4 phenylacetonitrile 
• 6393-50-6 α-lithiophenylacetonitrile 

Downstream Products

• 1351983-76-0 2-phenyl-2-(1,4-dioxaspiro[4.5]decan-7-yl)acetonitrile 
• 1351983-77-1 2-phenyl-2-(1,4-dioxaspiro[4.5]decan-7-yl)-acetaldehyde 

Relevant academic research and scientific papers

Access to 2-Amino-3-Arylthiophenes by Base-Catalyzed Redox Condensation Reaction Between Arylacetonitriles, Chalcones, and Elemental Sulfur

A straightforward access to 2-amino-3-arylthiophenes has been developed via one-pot two-step three-component reaction of arylacetonitriles, chalcones and elemental sulfur. The first step consists of a DBU-catalyzed formation of Michael adduct between aryl

Activation of nitriles by metal ligand cooperation. reversible formation of ketimido- and enamido-rhenium PNP pincer complexes and relevance to catalytic design

The dearomatized complex cis-[Re(PNPtBu*)(CO)2] (4) undergoes cooperative activation of Ci - N triple bonds of nitriles via [1,3]-addition. Reversible C-C and Re-N bond formation in 4 was investigated in a combined experimental and c

Solvent-free Michael addition of 2-cyclohexenone under ultrasonic irradiation in the presence of long chain dicationic ammonium salts

Long chain dicationic ammonium salts (1a-1c), easily prepared from tert-amines and dihaloalkanes, were successfully used as efficient phase-transfer catalysts in the Michael addition reaction of various active methylene compounds to 2-cyclohexenone withou

Design and scale-up of a practical enantioselective route to 5-Phenylbicyclo[2.2.2]oct-5-en-2-one

A practical enantioselective route to chiral 5-phenylbicyclo[2.2.2]oct-5- en-2-one 1 has been designed and developed. The target compound has been obtained as colorless crystals in 22% yield from 2-cyclohexenone, with an enantiomeric ratio higher than 99.5:0.5 and notably high chemical purity (> 99%). Three intermediates out of nine chemical steps are isolated. It is noteworthy that this process is devoid of any chromatography or distillation although all but one intermediate are oils. Key to success was the optimization of an intramolecular aldol reaction of an in situ prepared ketone aldehyde leading to the solid intermediate (1R,4R,4S,6S)-6-hydroxybicyclo[2.2.2]octan-2- one 9a that is isolated in very high chemical and chiral purity. This is an example of an intramolecular crystallization-induced diastereomer transformation (CIDT). The dehydration of this secondary alcohol to 1 required an extensive screen of reaction conditions to secure an excellent purity, essential for crystallization of this low-melting compound. The final process is simple and concentrated as demonstrated by an expeditious synthesis of 1 kg of 1 in a 30-L reactor in 10 working days.

Reconstructed hydrotalcite as a highly active heterogeneous base catalyst for carbon-carbon bond formations in the presence of water

The aldol reaction of carbonyl compounds is efficiently catalyzed by reconstructed hydrotalcites, obtained by treating the Mg-Al mixed oxide with water, as solid base catalysts in the presence of water. The catalysis of the reconstructed hydrotalcites is attributable to the surface base sites, created during the organization of the layered structure, with uniformly distributed strength. Furthermore, the reconstructed hydrotalcites provide a unique acid-base bifunctional surface capable of promoting the Knoevenagel and Michael reactions of nitriles with carbonyl compounds.

Water-soluble calixarenes as new inverse phase-transfer catalysts. Their application to aldol-type condensation and Michael addition reactions in water

Aldol-type condensation and Michael addition reactions of activated methyl and methylene compounds in aqueous NaOH solution have been developed without the need for any added organic solvents. The water-soluble calix[n]arenes, which contain trimethylammon

1,2- Vs 1,4-Regioselectivity of Lithiated Phenylacetonitrile toward α,βUnsaturated Carbonyl Compounds. 2. Relation between the Regioselectivity and the Structure of the Species in Solution

In THF and THF-toluene media, the reaction of lithiated phenylacetonitrile (1) with benzylide-neacetone (5), at low temperature, led to the same ratio of 1,2- and 1,4-adducts after 5 or 30 min of reaction time. The concentrations of the monomeric bridged ion pair 2 preferentially formed in THF and of the dimer of ion pairs 4 predominating in media that favor association such as THF-toluene solvent mixtures were measured from the IR-integrated intensities of the v (C≡N) bands. These concentrations were quantitatively related to the concentrations of the 1,2- and 1,4-adducts, respectively. All these results evidence the kinetic control of this reaction. Intermediate complexes that take into account the peculiar geometries of the monomer 2 and the dimer 4 are proposed to interpret the different regioselectivities observed with 5. This study is extended to cyclic α-enones and cinnamaldehyde. Similar trends hold for the former, while cinnamaldehyde always leads to 1,2-addition. The formation of intermediate complexes allows us to rationalize the cinnamaldehyde behavior but is insufficient to explain the 1,4-addition with cyclic α-enones lying in an s-trans conformation.

CONJUGATE ADDITION IN PHASE TRANSFER CATALYSIS CONDITIONS: REACTIONS OF α ENONES WITH ARYLACETONITRILES

Conjugate addition of arylacetonitriles 1-3 to α-enones 4-6 can be performed in liquid-liquid PTC conditions (toluene-saturated aqueous K2CO3 solution).The reaction is too slow with isophorone or mesityloxide to be synthetically useful.