229174-44-1

Upstream product

• 767-91-9 1-ethynyl-2-methoxybenzene 
• 619-44-3 methyl 4-iodobenzoate 
• 529-28-2 4-iodoanisol 
• 3034-86-4 4-ethynylbenzoic acid methyl ester 
• 40230-91-9 [(2-methoxyphenyl)ethynyl]trimethylsilane 
• 75867-41-3 4-trimethylsilanylethynyl-benzoic acid methyl ester 
• 5720-06-9 2-Methoxyphenylboronic acid 
• 253684-21-8 1,1-dibromo-2-(4-methoxycarbonylphenyl)ethene 

Relevant academic research and scientific papers

Low temperature Sonogashira coupling reaction

A low temperature Sonogashira reaction was developed, which coupled equimolar amount of aryl iodide possessing electron-withdrawing groups with aromatic acetylene at -20 °C in quantitative yield.

Acid-promoted selective synthesis of trifluoromethylselenolated benzofurans with Se-(trifluoromethyl) 4-methylbenzenesulfonoselenoate

A Br?nsted acid-promoted trifluoromethylselenolation of benzofurans was disclosed by using Se-(trifluoromethyl) 4-methylbenzenesulfonoselenoate as a stable and easily prepared electrophilic trifluoromethylselenolating reagent. A wide range of SeCF3-substituted benzofuran derivatives were obtained in moderate to good yields with excellent regioselectivity. The tandem cyclization/trifluoromethylselenolation procedure of 1-methoxy-2-(arylethynyl)benzenes were also realized by engaging FeCl3 as the catalyst.

CO-Free Enantioselective Hydroformylation of Functionalised Alkenes: Using a Dual Catalyst System to Give Improved Selectivity and Yield

The scope of carbon monoxide-free Asymmetric Transfer HydroFormylation (ATHF) procedures using a highly active single catalyst system derived from 1,2-bis-((2,5)-diphenylphospholano)ethane as chiral ligand has been studied. This reveals some highly successful reactions, but also significant limitations. The development of a new protocol in which a catalyst for formaldehyde decomposition to CO and H2 is combined with the catalyst of choice for the subsequent asymmetric hydroformylation is described. This enables ATHF reactions that were problematic to be significantly improved. The new method has been used in the synthesis of several key precursors to biologically active molecules. (Figure presented.).

Iridium-Catalyzed Intramolecular Methoxy C?H Addition to Carbon–Carbon Triple Bonds: Direct Synthesis of 3-Substituted Benzofurans from o-Methoxyphenylalkynes

Catalytic hydroalkylation of an alkyne with methyl ether was accomplished. Intramolecular addition of the C?H bond of a methoxy group in 1-methoxy-2-(arylethynyl)benzenes across a carbon–carbon triple bond took place efficiently either in toluene at 110 °C or in p-xylene at 135 °C in the presence of an iridium catalyst. The initial 5-exo cyclization products underwent double-bond migration during the reaction to give 3-(arylmethyl)benzofurans in high yields.

Can polarization of triple bond in tolanes be deduced from 13C NMR shifts? Re-evaluation of factors affecting regiochemistry of the palladium-catalyzed hydrostannation of alkynes

Polarization of the triple bond in a series of differently substituted ortho and para-tolanes has been studied by NMR and computational methods in order to examine if 13C NMR data can be effectively used for the assessment of electronic polarization of a triple bond in diarylacetylenes. DFT calculations of both natural charges and NMR properties revealed that chemical shifts concur with effective charges on sp-carbon atoms in para-tolanes, whereas in ortho-analogues magnetic anisotropy complicates the analysis making 13C NMR data inapplicable for ascribing triple bond polarization. The obtained information was used to reevaluate factors affecting the regiochemistry of the Pd-catalyzed hydrostannation of the triple bond in tolanes. Computational study on the polarization of triple bonds taken together with the experimental data on hydrostannation of various mono- and disubstituted tolanes bearing para- and ortho-substituents demonstrated that the regioselectivity of hydrostannation is governed by a combination of electronic and steric factors. In para-tolanes, the electronic effect prevails and α- and β-vinylstannanes are obtained predominantly for substrates with electron-withdrawing and electron-donating groups, respectively. In the ortho-series, steric factors dominate over electronics and α-isomers are produced with high selectivity regardless of the substituents' nature. However, it was found that in disubstituted "push-pull" tolanes steric control of an ortho-group can be overruled by the very strong electronic effect of an electron-withdrawing substituent in para-position.

Synthesis and preliminary testing of molecular wires and devices

Presented here are several convergent synthetic routes to conjugated oligo(phenylene ethynylene)s. Some of these oligomers are free of functional groups, while others possess donor groups, acceptor groups, porphyrin interiors, and other heterocyclic interiors for various potential transmission and digital device applications. The syntheses of oligo(phenylene ethynylene)s with a variety of end groups for attachment to numerous metal probes and surfaces are presented. Some of the functionalized molecular systems showed linear, wire-like, current versus voltage (I(V)) responses, while others exhibited nonlinear I(V) curves for negative differential resistance (NDR) and molecular random access memory effects. Finally, the syntheses of functionalized oligomers are described that can form self-assembled monolayers on metallic electrodes that reduce the Schottky barriers. Information from the Schottky barrier studies can provide useful insight into molecular alligator clip optimizations for molecuar electronics.

A modified Suzuki reaction of 1,1-dibromo-1-alkenes

The (E)-bromides in 1,1-dibromo-1-alkenes were stereoselectively coupled with aryl- or alkenylboronic acids to give the corresponding (Z)-1- Aryl(alkenyl)-1-bromo-1-alkenes. Tris(2-furyl)phosphine (TFP) was used as the ligand to palladium, and the combination of 1,4-dioxane and aqueous sodium carbonate produced the best results.