23594-02-7

Upstream product

• 20061-84-1 diethyl 2-(cyclohexylimino)ethylphosphonate 
• 90-98-2 4,4'-Dichlorobenzophenone 
• 121-44-8 triethylamine 
• 95269-22-0 ethyl 3,3-bis(4'-chlorophenyl)prop-2-enoate 
• 109-99-9 tetrahydrofuran 
• 7020-80-6 acetaldehyde N-tert-butylimine 
• 814-49-3 diethyl chlorophosphate 
• 5835-98-3 1,1-bis(4-chlorophenyl)-2-propyn-1-ol 
• 637-87-6 1-Chloro-4-iodobenzene 
• 75677-02-0 3-(4-chlorophenyl)propionaldehyde 
• 75-27-4 bromodichloromethane 
• 2642-81-1 1,1-bis(p-chlorophenyl)ethene 
• 123-38-6 propionaldehyde 
• 96089-74-6 3,3-bis-(4-chlorophenyl)prop-2-en-1-ol 

Downstream Products

• 120583-82-6 (E)-5,5-bis(4-chlorophenyl)-2,4-pentadienoic acid 
• 19618-36-1 3,3-bis(4-chlorophenyl)acrylic acid 
• 2540-35-4 3,3-bis-(4-chloro-phenyl)-propionic acid 
• 55589-49-6 6-chloro-3-(4-chloro-phenyl)-indan-1-one 
• 1318249-22-7 7-chloro-4-(4-chlorophenyl)quinoline 
• 22719-63-7 3-(2,2-diphenylvinyl)-1,1,5,5-tetraphenyl-1,4-pentadiene 

Relevant academic research and scientific papers

Deep eutectic solvent-catalyzed Meyer-Schuster rearrangement of propargylic alcohols under mild and bench reaction conditions

The Meyer-Schuster rearrangement of propargylic alcohols into α,β-unsaturated carbonyl compounds has been revisited by setting up an atom-economic process catalyzed by a deep eutectic solvent FeCl3·6H2O/glycerol. Isomerizations take place smoothly, at room temperature, under air and with short reaction times. The unique solubilizing properties of the eutectic mixture enabled the use of a substrate concentration up to 1.0 M with the medium being recycled up to ten runs without any loss of catalytic activity. This journal is

Copper-catalyzed formylation of alkenyl C-H bonds using BrCHCl2 as a stoichiometric formylating reagent

The first example of copper-catalyzed direct formylation of alkenyl C-H bonds for the facile synthesis of α,β-unsaturated aldehydes has been developed. This transformation has demonstrated high reactivity, mild reaction conditions and a broad substrate scope. BrCHCl2 is expected to be developed as an efficient stoichiometric C1 building block in organic synthesis.

Palladium-Catalyzed Cascade Saegusa–Heck Reaction: Synthesis of β,β-Diarylacroleins from Arylpropanals and Aryl Iodides

An efficient and convenient Pd-catalyzed Saegusa–Heck cascade protocol was developed, and its potential use in the synthesis of symmetrical and unsymmetrical β,β-diarylacroleins in moderate to high yields was investigated.

Phase-vanishing method applied to condensation reactions using TiCl4

The phase-vanishing (PV) method using perfluorohexanes as the phase screen was applied to the aldol condensation using TiCl4 as the Lewis acid. A special test tube was used, in which an interface between the fluorous and organic layers was stirred, and cyclohexanone was treated with two equivalents of benzaldehyde derivatives under PV conditions to afford corresponding 2,6-dibenzylidencyclohexanone in good yields. The formyl-methylenation of ketones with triethylamine using TiCl4 was also demonstrated by the PV method.

Metal- and Acid-Free Methyl Triflate Catalyzed Meyer-Schuster Rearrangement

A novel metal- and acid-free preparation of synthetically useful α,β-unsaturated carbonyl compounds from propargyl alcohols has been realized. This Meyer-Schuster rearrangement process is effectively catalyzed by methyl triflate (20 mol%) to prepare a broad scope of conjugated E -enals and E -enones generally in good to excellent yields (up to 90%). This reaction procedure operates under mild conditions (70 °C), in air, with short reaction times (1 h). Moreover, a carbocation intermediate trapped by the solvent 2,2,2-trifluoroethanol was isolated during this transformation.

A Weinreb Amide Based Building Block for Convenient Access to β,β-Diarylacroleins: Synthesis of 3-Arylindanones

Towards the synthesis of symmetrical and unsymmetrical β,β-diarylacroleins for assembling diarylmethine fragments present in biologically important molecules, we have developed a new Weinreb amide (WA) based building block, derived from propiolic acid. The WA functionality present in this compound allowed the sequential addition of various arylmagnesium bromide reagents in a controlled manner. The developed methodology for the access to β,β-diarylacroleins has been utilised for the synthesis of biologically important 3-arylindanone molecules. Synthesis of both symmetrical and unsymmetrical β,β-diarylacrolein and diarylmethine fragments, have been achieved via easily accessible and hitherto unknown Weinreb Amide (WA) based building block 11. The WA functionality allowed the sequential addition of nucleophiles such as arylmagnesium bromide in a controlled manner, which has enabled the synthesis of an important 3-arylindanone molecule.

Thermal intramolecular [2 + 2] cycloaddition: Synthesis of 3-azabicyclo[3.1.1]heptanes from morita-baylis-hillman adduct-derived 4,4-diaryl-1,3-dienes

Various 3-azabicyclo[3.1.1]heptane derivatives were synthesized from Morita-Baylis-Hillman adduct-derived 1,3-dienes bearing a 4,4-diaryl moiety through a thermal intramolecular [2+2] cycloaddition approach. By using the same approach, bicyclo[3.1.1]heptane, 3-azabicyclo[3.2.0]heptane, and 3-oxabicyclo[3.1.1]heptane derivatives could also be synthesized. A structurally similar dimethyl-Gallyl derivative underwent an intramolecular ene reaction to afford the pyrrolidine derivative.

Palladium-catalyzed dehydrogenative β-arylation of simple saturated carbonyls by aryl halides

(Chemical Equation Presented) A versatile palladium-catalyzed synthesis of highly substituted α,β-unsaturated carbonyl compounds has been developed. In contrast to the known Heck-type coupling reaction of unsaturated carbonyl compounds with aryl halides, the present methodology allows the use of stable and readily available saturated carbonyl compounds as the alkene source. In addition, the reaction proceeds well with low catalyst loadings and does not require any expensive metal oxidants or ligands. A variety of saturated aldehydes, ketones, and esters are compatible for the reaction with aryl halides under the developed reaction conditions to afford α,β-unsaturated carbonyl compounds in good to excellent yields. A possible reaction mechanism involves a palladium-catalyzed dehydrogenation followed by Heck-type cross couplings.

Synthesis and reactivity of new rhenium(I) complexes containing iminophosphorane-phosphine ligands: Application to the catalytic isomerization of propargylic alcohols in ionic liquids

[ReBr(CO)5] reacts with the iminophosphorane-phosphine ligands Ph2PCH2P(=NR)Ph2 (R = P(=O)(OEt)2 (1a), P(=O)(OPh)2 (1b), P(=S)(OEt)2 (1c), P(=S)(OPh) 2 (1d), 4-C6F4CHO (1e), 4-C6F 4CN (1f), 4-C5F4N (1g)) affording the neutral complexes [ReBr(κ2-P,X-Ph2PCH2P{=NP(=X) (OR)2}Ph2)(CO)3] (X = O, R = Et (2a), Ph (2b); X = S, R = Et (2c), Ph (2d)) and [ReBr{κ2-P,N-Ph 2PCH2P(=NR)Ph2}(CO)3] (R = P(=O)(OEt)2 (3a), P(=O)(OPh)2 (3b), 4-C6F 4CHO (3e), 4-C6F4CN (3f), 4-C5F 4N (3g)). The reactivity of the cationic complex [Re(κ 3-P,N,S-Ph2PCH2P{=NP(=S)(OPh) 2}Ph2)(CO)3][SbF6] (4d) has been explored allowing the synthesis of the cationic [Re(L)(κ2-P,S- Ph2PCH2P{=NP(=S)(OPh)2}Ph2)(CO) 3][SbF6] (L = acetone (5a), CH3C≡N (5b), pyridine (5c), PPh3 (5d)) and the neutral [ReY(κ2-P, S-Ph2PCH2P{=NP(=S)(OPh)2}Ph2)(CO) 3] (Y = Cl (6a), I (6b), N3 (6c)) complexes. The catalytic activity of complex 4d in the regioselective isomerization of terminal propargylic alcohols HC≡CCR1R2(OH) into α,β-unsaturated aldehydes R1R2C=CHCHO or ketones R3R4C=CR1COMe (if R2 = CHR3R4) under neutral conditions in ionic liquids has being studied. Isolation and X-ray characterization of the key intermediate rhenium(I) oxocyclocarbene complex [Re{=C(CH2)3O} (κ2-P,S-Ph2PCH2P{=NP(=S)(OPh) 2}Ph2)(CO)3][SbF6] (5e) seems to indicate that the catalytic reaction proceeds through tautomerization of the terminal alkynols to yield vinilydene-type species.

Novel rhenium(i) catalysts for the isomerization of propargylic alcohols into α,β-unsaturated carbonyl compounds: An unprecedented recyclable catalytic system in ionic liquids

Carbonyl rhenium(i) complexes are efficient catalysts for the regioselective isomerization of terminal propargylic alcohols into α,β-unsaturated aldehydes or ketones which can be used as an unprecedented recyclable catalytic system (up to 10 consecutive runs) in the ionic liquid [BMIM][PF6].