125261-30-5

Upstream product

• 120-47-8 Ethyl 4-hydroxybenzoate 
• 358-23-6 trifluoromethylsulfonic anhydride 
• 939050-79-0 ethyl 3-chloro-4-{[(trifluoromethyl)sulfonyl]oxy}benzoate 
• 78888-18-3 N-tert-butoxycarbonylprop-2-en-1-amine 
• 4334-88-7 p-ethoxycarbonylphenylboronic acid 
• 2926-30-9 sodium triflate 
• 99-96-7 4-hydroxy-benzoic acid 
• 902148-89-4 ethyl 4-(methanesulfonyloxy)benzoate 
• 66107-30-0 4-bromophenyl trifluoromethanesulfonate 
• 17763-67-6 Phenyl triflate 
• 109586-39-2 4-iodophenyl trifluoromethanesulfonate 
• 623-49-4 ethyl cyanoformate 

Downstream Products

• 93-89-0 benzoic acid ethyl ester 
• 195062-62-5 ethyl 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)benzoate 
• 197662-64-9 ethyl 1,2,4,5-tertafluoro-3-methoxybenzene 
• 5798-75-4 Ethyl 4-bromobenzoate 
• 38430-55-6 ethyl-4-acetylbenzoate 
• 1393538-92-5 2-(p-ethoxycarbonylphenyl)-1-octene 
• 30058-58-3 1-(p-ethoxycarbonylphenyl)cycloheptene 
• 1461737-17-6 (S)-2-[p-(ethoxycarbonyl)phenyl]-2,5-dihydrofuran 
• 15165-27-2 ethyl 4-benzoylbenzoate 
• 51934-41-9 4-iodobenzoic acid ethyl ester 
• 713-57-5 terephthalic acid monoethyl ester 
• 38628-52-3 3-(4-(ethoxycarbonyl)phenyl)propanoic acid ethyl ester 
• 47230-38-6 diethyl biphenyl-4,4'-dicarboxylate 
• 94-08-6 4-methylbenzoic acid ethyl ester 

Relevant academic research and scientific papers

Bismuth-Catalyzed Oxidative Coupling of Arylboronic Acids with Triflate and Nonaflate Salts

Herein we present a Bi-catalyzed cross-coupling of arylboronic acids with perfluoroalkyl sulfonate salts based on a Bi(III)/Bi(V) redox cycle. An electron-deficient sulfone ligand proved to be key for the successful implementation of this protocol, which allows the unusual construction of C(sp2)-O bonds using commercially available NaOTf and KONf as coupling partners. Preliminary mechanistic studies as well as theoretical investigations reveal the intermediacy of a highly electrophilic Bi(V) species, which rapidly eliminates phenyl triflate.

Practical Ni-Catalyzed Cross-Coupling of Unsaturated Zinc Pivalates with Unsaturated Nonaflates and Triflates

A practical nickel-catalyzed cross-coupling of (hetero)aryl or alkynylzinc pivalates with various unsaturated nonaflates or triflates is described. Organozinc pivalates allow these cross-couplings to take place with high yields and a low catalyst loading (0.5 mol %). Couplings with (E)- and (Z)-alkenyl triflates proceed with retention of configuration.

Palladium-Catalyzed Chemoselective Negishi Cross-Coupling of Bis[(pinacolato)boryl]methylzinc Halides with Aryl (Pseudo)Halides

We describe a palladium-catalyzed chemoselective Negishi cross-coupling of a bis[(pinacolato)boryl]methylzinc halide with aryl (pseudo)halides. This reaction affords an array of benzylic 1,1-diboronate esters, which can serve as useful synthetic handles f

Barbier–Negishi Coupling of Secondary Alkyl Bromides with Aryl and Alkenyl Triflates and Nonaflates

A mild and practical Barbier–Negishi coupling of secondary alkyl bromides with aryl and alkenyl triflates and nonaflates has been developed. This challenging reaction was enabled by the use of a very bulky imidazole-based phosphine ligand, which resulted in good yields as well as good chemo- and site selectivities for a broad range of substrates at room temperature and under non-aqueous conditions. This reaction was extended to primary alkyl bromides by using an analogous pyrazole-based ligand.

Directed ortho Metalation (D o M)-Linked Corriu-Kumada, Negishi, and Suzuki-Miyaura Cross-Coupling Protocols: A Comparative Study

A systematic study of the widely used, titled name reaction transition-metal-catalyzed cross-coupling reactions with attention to context with the directed ortho metalation (D o M) is reported. In general, the Suzuki-Miyaura and Negishi protocols show gre

Synthesis of 9,10-Diarylanthracenes via Mg(TMP) 2 ·2LiCl-Mediated Benzyne Generation/[4+2] Cycloaddition and Deoxygenation of 9,10-Epoxyanthracene Intermediates

A new synthetic route to functionalized 9,10-diarylanthracenes has been developed. 9,10-Epoxyanthracene intermediates were prepared by [4+2] cycloaddition of 1,3-diarylisobenzofuran with a variety of functionalized benzyne intermediates, which were obtained by Mg(TMP) 2 ·2LiCl-mediated benzyne generation. For the cleavage of the resultant 9,10-epoxyanthracene intermediates, we developed mild deoxygenation conditions using a combination of trifluoroacetic acid and Et 3 SiH. The utility of this sequence was demonstrated by application to the synthesis of 5,7,12,14-tetraphenylpentacene.

Highly active catalysts of bisphosphine oxides for asymmetric Heck reaction

Bisphosphine oxides formed highly active asymmetric Heck catalysts, which were applied in asymmetric synthesis of pharmacologically active azacycles. Olefin insertion proceeded via cis pathways, different from P,N-ligands.

Selective arylation and vinylation at the α position of vinylarenes

In intermolecular Heck reactions of styrene and vinylarenes, the aryl and vinyl groups routinely insert at the β position. However, selective insertion at the α position has been very rare. Herein, we provide a missing piece in the palette of Heck reaction, which gave >20:1 α selectivity. The key to our success is a new ferrocene 1,1′-bisphosphane (dnpf) that carries 1-naphthyl groups. Our mechanistic studies revealed that the high α selectivity is partly attributable to the steric effect of dnpf. The rigid and bulky 1-naphthyl groups of dnpf sterically disfavor β insertion. What the Heck! In intermolecular Heck reactions, insertion at the β position of aromatic olefins is very common, but reversal of the selectivity for selective α insertion has been a longstanding problem. A general method to couple aryl and vinyl triflates with aromatic olefins in >20:1 α selectivity is presented. The key to this successful approach is a new ferrocene bisphosphane with naphthyl groups on the phosphorus atom (see scheme; OTf=triflate). Copyright

Achieving vinylic selectivity in Mizoroki-heck reaction of cyclic olefins

In Heck reactions of cyclic olefins, the products usually have aryl groups that end up at the allylic and/or homoallylic position. We herein report new selectivity that adds aryl groups to the vinylic position. Cyclic olefins of various ring size worked well. The desired isomers were produced by palladium-hydride-catalyzed isomerization of the initial products. Thus, a specific catalyst must be used so that it can perform two jobs under one set of reaction conditions. Copyright

CHIRAL PHOSPHINES FOR PALLADIUM-CATALYZED ASYMMETRIC ALPHA-ARYLATION OF ESTER ENOLATES TO PRODUCE TERTIARY STEREOCENTERS IN HIGH ENANTIOSELECTIVITY

The disclosure provides new and improved methods for the Pd-catalyzed asymmetric α-arylation of ester compounds, which produce the corresponding α-aryl moiety in high enantioselectivity (generally >90% ee). The present methods utilize a palladium catalyst supported by new (R)-H8-BINOL-derived monophosphine ligands. The method is applicable to a wide variety of aryl triflate substrates having variations in both electronic and steric properties. These aryl triflate substrates react with various α-alkyl (Z)- and/or (E)-0-trimethylsilyl ketene acetals in the presence of a Pd catalyst, (R)-H8-BINOL-derived monophosphine ligand, and a mild activator, for example, LiOAC, to provide the asymmetric α-arylation of ester compounds in high ee.