129182-23-6

Upstream product

• 104-92-7 1-bromo-4-methoxy-benzene 
• 111-66-0 oct-1-ene 
• 696-62-8 para-iodoanisole 
• 134837-65-3 1-octenyltriethoxysilane 
• 66107-29-7 4-methoxyphenyl triflate 
• 150-76-5 4-methoxy-phenol 
• 623-12-1 4-chloromethoxybenzene 
• 5720-07-0 4-methoxyphenylboronic acid 
• 69287-13-4 1-(4-methoxyphenyl)-1-heptanone 
• 1779-49-3 Methyltriphenylphosphonium bromide 
• 775-27-9 4-methoxyphenyl sulfurofluoridate 
• 57404-76-9 trans-1-heptenylboronic acid 
• 129182-18-9 (ethyl)(difluoro)(4-methoxyphenyl)silane 
• 98747-02-5 oct-1-en-2-yl trifluoromethanesulfonate 

Relevant academic research and scientific papers

Iron-Catalyzed Highly Enantioselective Hydrogenation of Alkenes

Here, we reported for the first time an iron-catalyzed highly enantioselective hydrogenation of minimally functionalized 1,1-disubstituted alkenes to access chiral alkanes with full conversion and excellent ee. A novel chiral 8-oxazoline iminoquinoline ligand and its iron complex have been designed and synthesized. This protocol is operationally simple by using 1 atm of hydrogen gas and shows good functional group tolerance. A primary mechanism has been proposed by the deuterium-labeling experiments.

An Electrochemically Promoted, Nickel-Catalyzed Mizoroki-Heck Reaction

Despite significant efforts to replace Pd-based catalysts with those of Ni, the Ni-catalyzed Mizoroki-Heck coupling of aryl halides and alkenes remains challenging. This work details the development of a Mizoroki-Heck reaction of aryl halides and a broad range of alkenes that utilizes electrochemistry as a means to promote Ni-catalyzed coupling under mild conditions. Stoichiometric studies implicate low-valent Ni complexes as key intermediates in route to rapid reactions with even unactivated alkenes. As such, electrochemistry is employed to readily provide the reducing potentials necessary to access these reactive intermediates and render the transformation catalytic. Cyclohexenone was found to be an unreactive substrate but a crucial additive that promotes facile electroreduction of the Ni catalyst and functionalization of other alkenes in high yields. Finally, preliminary mechanistic studies suggest that reactions proceed via an electron-chain transfer process that rapidly terminates but is reinitiated upon electroreduction.

METHOD FOR COUPLING A FIRST COMPOUND TO A SECOND COMPOUND

The present disclosure describes a method of coupling a first compound to a second compound, the method comprising: providing the first compound having a fluorosulfonate substituent; providing the second compound comprising an alkene; and reacting the first compound and the second compound in a reaction mixture, the reaction mixture including a catalyst having at least one group 10 atom, the reaction mixture under conditions effective to couple the first compound to the second compound.

Regioselective aerobic oxidative Heck reactions with electronically unbiased alkenes: Efficient access to α-alkyl vinylarenes

Branched-selective oxidative Heck coupling reactions have been developed between arylboronic acids and electronically unbiased terminal alkenes. The reactions exhibit high catalyst-controlled regioselectivity favoring the less common branched isomer. The reactions employ a catalyst composed of Pd(TFA)2/dmphen (TFA = trifluoroacetate, dmphen = 2,9-dimethyl-1,10-phenanthroline) and proceed efficiently at 45-60 °C under 1 atm of O2 without requiring other additives. A broad array of functional groups, including aryl halide, allyl silane and carboxylic acids are tolerated.

Nickel-catalyzed Mizoroki-Heck reaction of aryl sulfonates and chlorides with electronically unbiased terminal olefins: High selectivity for branched products

Achieving high selectivity in the Heck reaction of electronically unbiased alkenes has been a longstanding challenge. Using a nickel-catalyzed cationic Heck reaction, we were able to achieve excellent selectivity for branched products (≥19:1 in all cases) over a wide range of aryl electrophiles and aliphatic olefins. A bidentate ligand with a suitable bite angle and steric profile was key to obtaining high branched/linear selectivity, whereas the appropriate base suppressed alkene isomerization of the product. Although aryl triflates are traditionally used to access the cationic Heck pathway, we have shown that, by using triethylsilyl trifluoromethanesulfonate, we can effect a counterion exchange of the catalytic nickel complex, such that cheaper and more stable aryl chlorides, mesylates, tosylates, and sulfamates can be used to yield the same branched products with high selectivity. Branching out: A Ni-catalyzed Heck reaction for the preparation of 1,1-disubstituted alkenes is presented. High selectivity for the branched products is achieved with electronically unbiased aliphatic terminal olefins. Regioselectivities remain consistently high (≥19:1) throughout. TESOTf=triethylsilyl trifluoromethanesulfonate. Copyright

Intermolecular mizoroki-heck reaction of aliphatic olefins with high selectivity for substitution at the internal position

New ligand for old reaction: The title reaction of aryltriflates with aliphatic olefins leads to substitution at the internal position with high selectivity. The ratio of the desired isomer (shown in the scheme) to the sum of all other isomers is generall

Oxime palladacycle-catalyzed Suzuki-Miyaura alkenylation of aryl, heteroaryl, benzyl, and allyl chlorides under microwave irradiation conditions

A simple new protocol for the palladium-catalyzed Suzuki-Miyaura cross-coupling of organic chlorides under microwave irradiation is presented. Deactivated aryl and heteroaryl chlorides are efficiently cross-coupled with alkenylboronic acids and potassium alkenyltrifluoroborates using the 4,4′-dichlorobenzophenone oxime-derived palladacycle 1b as precatalyst in 0.1 to 0.5 mol% palladium loading, tris(tert-butyl)phosphonium tetrafluoroborate {[HP(t-Bu)3]BF4} as ligand, tetra-n-butylammonium hydroxide as cocatalyst, and potassium carbonate as base in N,N- dimethylformamide at 130°C under microwave irradiation conditions. Under these conditions, styrenes, stilbenes, and alkenylarenes are obtained in good to high yields, and with high regio- and diastereoselectivities in only 20 min. The reported protocol is also very efficient for the regioselective alkenylation of benzyl and allyl chlorides to afford allylarenes and 1,4-dienes. Copyright

Aqueous sodium hydroxide promoted cross-coupling reactions of alkenyltrialkoxysilanes under ligand-free conditions

(Chemical Equation Presented) Fluoride-free cross-coupling reactions of alkenyltrialkoxysilanes with aryl iodides, bromides, and chlorides are performed on water using sodium hydroxide as activator at 120 °C under normal or microwave heating. This process occurs in the presence of Pd(OAc)2 or 4-hydroxyacetophenone oxime-derived palladacycle 1 as precatalysts under ligand-free conditions with low Pd loadings (0.01-1 mol %) and using tetra-n-butylammonium bromide as additive. Different commercially available vinylalkoxylsilanes can be cross-coupled under these reaction conditions to the corresponding styrenes, the best substrates being vinyltrimethoxy- or vinyltriethoxysilane. Alkenyltriethoxysilanes, prepared by Wilkinson-catalyzed hydrosilylation of alkynes with triethoxysilane, are stereospecifically arylated with aryl and vinyl halides under microwave irradiation in moderate to high β/α regioselectivity affording unsymmetrical stilbenes, alkenylbenzenes, and conjugate dienes, respectively. This simple procedure allows the palladium recycling from the aqueous phase during three runs by extractive separation of the products, which contain very low levels of Pd (21-27.5 ppm for an aryl iodide and up to 76 ppm for a bromide).

Palladium-tetraphosphine catalysed heck reaction with simple alkenes: Influence of reaction conditions on the migration of the double bond

The Heck reaction of aryl halides with simple alk-1-enes is a powerful method for the synthesis of (E)-1-arylalk-1-ene derivatives. The major problem of this reaction is the palladium-catalysed migration of the carbon-carbon double bond along the alkyl ch

A wide range of organosilicon compounds couples with enol and aryl triflates in the presence of Pd catalyst and fluoride ion

Under the influence of tetrakis(triphenylphosphine)palladium and tetrabutylammonium fluoride, the title reaction took place with alkenyl, alkynyl, aryl, and alkylsilanes to give the corresponding coupled products in good yields with high chemoselectivity and stereospecificity.