98921-99-4

Upstream product

• 459-64-3 4-methoxybenzenediazonium tetrafluoroborate 
• 292638-85-8 acrylic acid methyl ester 
• 3901-07-3 3-(4-methoxy-phenyl)acrylic acid methyl ester 
• 100-66-3 methoxybenzene 
• 90-96-0 bis(p-methoxyphenyl)methanone 
• 21204-67-1 methyl (triphenylphosphoranylidene)acetate 
• 104-92-7 1-bromo-4-methoxy-benzene 
• 7515-17-5 methyl 3-(4-methoxyphenyl)propynoate 
• 696-62-8 para-iodoanisole 
• 98921-98-3 1,1-dimethoxy-2-bromoethylene 
• 958-80-5 bis(4-methoxyphenyl)thione 
• 77-78-1 dimethyl sulfate 
• 832-01-9 methyl p-methoxycinnamate 
• 1067-74-9 Methyl diethylphosphonoacetate 

Downstream Products

• 90-96-0 bis(p-methoxyphenyl)methanone 
• 17792-18-6 3,3-bis(4-methoxyphenyl)propenoic acid 

Relevant academic research and scientific papers

Expedient Synthesis of Heterobifunctional Triarylmethane Stoppers for Macromolecular Rotaxanes

Increasingly complex rotaxane-based molecular devices are interfaced with polymers and surfaces, but suitable bifunctional stoppering groups are lacking. Here, we report a two-step, high-yielding synthesis toward a new class of heterobifunctional triarylmethane stoppers. They possess hydroxyl and ester groups for further functionalization as well as halogen substituents conferring a diagnostic spectroscopic signature. Their utility was demonstrated with the synthesis of a chain-centered macromolecular rotaxane. This new stopper architecture should prove useful to connect rotaxanes with polymers and surfaces for applications in polymer mechanochemistry, single-molecule force spectroscopy, smart materials, and molecular machines.

“Haliranium Ion”-Induced Intermolecular Friedel-Crafts Alkylation in HFIP: Synthesis of β,β-Diaryl α-Halo carbonyl Compounds

Here reports a highly regio- and diastereoselective haliranium ion-induced intermolecular Friedel-Crafts reaction of α,β-unsaturated carbonyl compounds in HFIP. The operationally simple and mild method affords the synthetically useful β,β-diarylated α-hal

In Situ Generated Palladium on Aluminum Phosphate as Catalytic System for the Preparation of β,β-Diarylated Olefins by Matsuda-Heck Reaction

In situ generated palladium on aluminum phosphate provides a novel and active catalytic system for the preparation of β,β-diarylated olefins using the Matsuda-Heck reaction. The reaction conditions of this catalytic protocol were optimized by a Response-Surface model.

Hg(II) and Pd(II) complexes with a new selenoether bridged biscarbene ligand: Efficient mono- and bis-arylation of methyl acrylate with a pincer biscarbene Pd(II) precatalyst

Two equivalents of 1-benzyl-3-bromoethylbenzimidazolium bromide couple with Na2Se to produce the first selenoether bridged bis-benzimidazolium salt (LH2)Br2. The nitrate (LH2)(NO3)2 and tetrafluoroborate (LH2)(BF4)2 salts were also synthesized from (LH2)Br2. The reaction of Hg(OAc)2 with (LH2)Br2 gave the first pseudo pincer carbene mercury complex, [Hg(L-κ2C)][HgBr4] (C1). Different complexes of Pd(ii) with selenoether bridged carbene were obtained using (LH2)Br2 and (LH2)(NO3)2. Syntheses of these complexes were dependent on the counter anion and the temperature. Thus, the pincer type ionic complex [PdBr(L-κ3CSeC)]Br (C2) was isolated at 80 °C and the pseudo pincer type neutral complex cis-[PdBr2(L-κ2C)] (C3) was isolated at room temperature from (LH2)Br2 and Pd(OAc)2 in DMSO. The nitrate precursor (LH2)(NO3)2 on palladation with Pd(OAc)2 afforded [Pd(L-κ4CBzCSeC)]NO3 (C4) showing an unprecedented intramolecular metallation at the ortho position of the benzyl wingtip of the benzimidazole moiety. The ligand salts and metal complexes have been characterized using HRMS, heteronuclear NMR and IR spectroscopy. Single crystal X-ray structures of the ligand salts (LH2)Br2 and (LH2)(BF4)2 and complexes C1-C4 have also been elucidated. Complex C2 showed good activity for C-C coupling in the mono-Heck reaction of methyl acrylate and arylbromides. Interestingly, the less common bis-arylation was also observed with deactivated arylbromides as the result of double-Heck coupling.

An in Situ Generated Palladium on Aluminum Oxide: Applications in Gram-Scale Matsuda-Heck Reactions

In situ generated palladium on aluminum oxide provides an active catalytic system for Matsuda-Heck reactions in gram-scale. The novel catalyst proceeded through a significantly higher catalytic activity compared to the classical Pd/C system. Based on the high catalytic activity the first α,β,β-triarylation of methyl acrylate in good yields could be provided in one-step.

Synthesis of arylethylene or diarylethylene compounds by Pd-catalyzed heck coupling reaction

We have developed an effective palladium-catalyzed arylation or diarylation couplings of olefins with various aryl halides in the presence of readily available ligands. This method is simple, economical, and practical for the synthesis of arylethylene and diarylethylene. Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications for full experimental and spectral details.

Facile synthesis of symmetrical 3,3-diarylacrylates by a Heck-Matsuda reaction: An expedient route to biologically active indanones

A simple and straightforward synthesis of symmetrical 3,3-diarylacrylates based on a Heck-Matsuda reaction of arenediazonium salts bearing electron-donating groups with methylacrylates is described. The reaction employs Pd(OAc)2 as catalyst and goes to completion within 1 h affording the corresponding unsaturated diaryl esters in good to high yields. This method permitted the expeditious and efficient synthesis of the anticancer 3-arylindanone 5 in two operative steps in 43% overall yield.

Stereoselective synthesis of unsymmetrical β,β-diarylacrylates by a heck-matsuda reaction: Versatile building blocks for asymmetric synthesis of β,β-diphenylpropanoates, 3-Aryl-indole, and 4-Aryl-3,4-dihydro- quinolin-2-one and formal synthesis of (-)-indatraline

β,β-Disubstituted R,β-unsaturated esters may serve as valuable derivatives for the preparation of other highly functionalized systems found in many natural products and marketed drugs. The stereoselective synthesis of unsymmetrical β,β-diarylacrylate compounds possessing two similar aromatic groups remains a substantial challenge. A simple and convenient stereoselective protocol for the preparation of β,β- disubstituted acrylates via a Heck-Matsuda reaction is reported. Good to high yields were accomplished by a "ligand-free" Pd-catalyzed arylation reaction of cinnamate esters with arenediazonium tetrafluoroborates. Both electron-deficient and electron-rich arenediazonium salts could be employed as arylating reagents, and cinnamate esters were generally more reactive when substituted with an electron-donating group. The overall methodology is highly stereoselective, and this attribute was taken advantage of in the asymmetric Cu-catalyzed 1,4 reduction reaction to provide β,β-diarylpropanoates in high enantioselectivities. The synthesis of a 3-aryl indole and a chiral 4-aryl-2-quinolone from β,β-diarylacrylates was achieved by cyclization in the presence of a diphosphine ligated CuH catalyst. A convenient route for the asymmetric formal synthesis of the psychoactive compound (-)-Indatraline is also presented.

Synthesis of substituted styrenes and stilbenes mediated by palladium on zirconia

Palladium on zirconia has been found to be an effective catalyst for the synthesis of various substituted styrenes and stilbenes, including biologically active natural products, by reaction of aryl halides with olefins.

Reactions of vinyl type carbocations generated in fluorosulfonic acid with benzene derivatives. New synthesis of alkyl 3,3-diarylpropenoates

Vinyl type carbocations ArC+=CHX [X = CO2H, CO 2Alk, C≡N, P(O)(OAlk)2] generated from alkyl 3-arylpropynoates and related compounds in fluorosulfonic acid at -75 to -20°C react with various benzene derivatives,