18322-84-4

Upstream product

• 18322-78-6 2-(trans-2-butenyl)phenol 
• 77-78-1 dimethyl sulfate 
• 100-66-3 methoxybenzene 
• 121197-99-7 crotyl tripropyl pyrophosphate 
• 121197-89-5 P₁,P₂-dicrotyl P₁,P₂-dipropyl pyrophosphate 
• 106-99-0 buta-1,3-diene 
• 13139-86-1 4-methoxyphenyl magnesium bromide 
• 563-52-0 2-chloro-3-butene 
• 3815-30-3 4-(4-methoxyphenyl)-3-buten-2-one 
• 4894-61-5 trans-but-2-enyl chloride 
• 696-62-8 para-iodoanisole 
• 20574-98-5 4-(p-methoxyphenyl)but-1-ene 
• 104-92-7 1-bromo-4-methoxy-benzene 
• 623-12-1 4-chloromethoxybenzene 

Downstream Products

• 53917-01-4 1-(4-methoxyphenyl)butan-2-one 

Relevant academic research and scientific papers

Selecting double bond positions with a single cation-responsive iridium olefin isomerization catalyst

The catalytic transposition of double bonds holds promise as an ideal route to alkenes of value as fragrances, commodity chemicals, and pharmaceuticals; yet, selective access to specific isomers is a challenge, normally requiring independent development of different catalysts for different products. In this work, a single cation-responsive iridium catalyst selectively produces either of two different internal alkene isomers. In the absence of salts, a single positional isomerization of 1-butene derivatives furnishes 2-alkenes with exceptional regioselectivity and stereoselectivity. The same catalyst, in the presence of Na+, mediates two positional isomerizations to produce 3-alkenes. The synthesis of new iridium pincer-crown ether catalysts based on an aza-18-crown-6 ether proved instrumental in achieving cation-controlled selectivity. Experimental and computational studies guided the development of a mechanistic model that explains the observed selectivity for various functionalized 1-butenes, providing insight into strategies for catalyst development based on noncovalent modifications.

Mild olefin formationviabio-inspired vitamin B12photocatalysis

Dehydrohalogenation, or elimination of hydrogen-halide equivalents, remains one of the simplest methods for the installation of the biologically-important olefin functionality. However, this transformation often requires harsh, strongly-basic conditions, rare noble metals, or both, limiting its applicability in the synthesis of complex molecules. Nature has pursued a complementary approach in the novel vitamin B12-dependent photoreceptor CarH, where photolysis of a cobalt-carbon bond leads to selective olefin formation under mild, physiologically-relevant conditions. Herein we report a light-driven B12-based catalytic system that leverages this reactivity to convert alkyl electrophiles to olefins under incredibly mild conditions using only earth abundant elements. Further, this process exhibits a high level of regioselectivity, producing terminal olefins in moderate to excellent yield and exceptional selectivity. Finally, we are able to access a hitherto-unknown transformation, remote elimination, using two cobalt catalysts in tandem to produce subterminal olefins with excellent regioselectivity. Together, we show vitamin B12to be a powerful platform for developing mild olefin-forming reactions.

Controllable Isomerization of Alkenes by Dual Visible-Light-Cobalt Catalysis

We report herein that thermodynamic and kinetic isomerization of alkenes can be accomplished by the combination of visible light with Co catalysis. Utilizing Xantphos as the ligand, the most stable isomers are obtained, while isomerizing terminal alkenes over one position can be selectively controlled by using DPEphos as the ligand. The presence of the donor–acceptor dye 4CzIPN accelerates the reaction further. Transformation of exocyclic alkenes into the corresponding endocyclic products could be efficiently realized by using 4CzIPN and Co(acac)2 in the absence of any additional ligands. Spectroscopic and spectroelectrochemical investigations indicate CoI being involved in the generation of a Co hydride, which subsequently adds to alkenes initiating the isomerization.

Reactivity of mixed organozinc and mixed organocopper reagents: 14. Phosphine-nickel catalyzed aryl-allyl coupling of (n-butyl)(aryl)zincs. Ligand and substrate control on the group selectivity and regioselectivity

The group selectivity and regioselectivity in the allylation of mixed (n-butyl)(aryl)zinc reagents in THF depends on the nickel catalyst type and also on nature of the allylic substrate. Allylation of (n-butyl)(phenyl)zinc reagent with alkyl substituted primary allylic chlorides and acetates in the presence of NiCl2(dppf) catalysis affords the phenyl coupling product with γ-selectivity. However, allylation with aryl substituted primary allylic substrates results in both phenyl- and alkyl-coupling products with medium α-selectivity in the presence of NiCl2(dppf) catalysis whereas phenyl coupling product is formed with α-selectivity in the presence of NiCl2(Ph3P)2 catalysis. This new NiCl2(dppf) catalyzed protocol for γ-selective aryl allylation of (n-butyl)(aryl)zinc reagents with alkyl substituted primary allylic chlorides in THF at room temperature provides an atom economic alternative to allylation of (aryl)2Zn reagents. A mechanism for the dependence of group selectivity and regioselectivity of Ni catalyzed allylation of (n-butyl)(aryl)zinc reagents on the catalyst ligand and the substrate was proposed.

The aromatic production of olefins

PROBLEM TO BE SOLVED: To provide a method for efficiently producing aromatic olefins useful for various functional chemicals.SOLUTION: Aromatic olefins are produced by reaction of an aromatic compound with an epoxide or aldehyde in the presence of a solid

Synthesis of enantioenriched alkylfluorides by the fluorination of boronate complexes

The enantiospecific conversion of chiral secondary boronic esters into alkylfluorides is reported. Boronate complexes derived from boronic esters and PhLi were used as nucleophiles, with Selectfluor II as the electrophilic fluorinating agent, to afford alkylfluorides in short reaction times. The addition of styrene as a radical trap was found to enhance enantiospecificity. A broad range of alkyl boronic esters were converted into alkylfluorides with almost complete enantiospecificity by this method.

Reactivity of mixed organozinc and mixed organocopper reagents: 11. Nickel-catalyzed atom-economic aryl-allyl coupling of mixed (n-alkyl)(aryl)zincs

Group selectivity in the allylation of mixed (n-butyl)(phenyl)zinc reagent can be controlled by changing reaction parameters. CuCN-catalyzed allylation in tetrahydrofuran (THF)-hexamethylphosphoric triamide is n-butyl selective and also γ-selective in the presence of MgCl2, whereas CuI-catalyzed allylation in THF in the presence of n-Bu3P takes place with a n-butyl transfer:phenyl transfer ratio of 23:77 and an α:γ transfer ratio of phenyl of 76:24. NiCl2(Ph3P) 2-catalyzed allylation in the presence of LiCl is phenyl selective with an α:γ ratio of 65:35. The reaction of methyl- or n-butyl(aryl)zinc reagents with an allylic electrophile in THF at room temperature in the presence of NiCl2(Ph3P)2 catalyst and LiCl as an additive provides an atom-economic alternative to aryl-allyl coupling using diarylzincs. Copyright

Multimetallic Ir-Sn3-catalyzed substitution reaction of π-activated alcohols with carbon and heteroatom nucleophiles

An atom economic and catalytic substitution reaction of π-activated alcohols by a multimetallic IreSn3 complex has been demonstrated. The multimetallic IreSn3 complex can be easily synthesized from the reaction between [Cp*IrCl2]2 and SnCl2. In presence of as little as 1 mol % of the catalyst three different types of π-activated alcohols, namely benzyl, allyl, and propargyl alcohols, have been successfully transformed into alkylated products using carbon (arenes, heteroarenes, allyltrimethylsilane, and 1,3-dicarbonyls), nitrogen (sulfonamides), oxygen (alcohols), and sulfur (thiols) nucleophiles in very high yields. An electrophilic mechanism is proposed from the Hammett correlation study.

Nickel-catalyzed reductive allylation of aryl bromides with allylic acetates

This paper highlights Ni-catalyzed allylation of electron-rich aryl bromides with a variety of substituted allylic carbonates using zinc as the terminal reductant, affording E-alkenes regioselectively in good to excellent yields by the addition of aryl to the less hindered allylic carbon. The electron-deficient aryl bromides and chlorides are also highly efficient coupling partners. The Royal Society of Chemistry 2013.

Method for Allylating and Vinylating Aryl, Heteroaryl, Alkyl, and Alkene Halogenides Using Transition Metal Catalysis

What is described is a process for preparing organic compounds of the general formula (I) R—R′??(I) by converting a corresponding compound of the general formula (II) R—X ??(II) in which X is fluorine, chlorine, bromine or iodine to an organomagnesium compound of the general formula (III) [M+]n[RmMgXkY1]??(III) wherein compounds of the formula (III) are reacted with a compound of the general formula (IV) characterized in that the reaction of (III) with (IV) is performed in the presence of a) catalytic amounts of an iron compound, based on the compound of the general formula (II), and optionally in the presence of b) a nitrogen-, oxygen- and/or phosphorus-containing additive in a catalytic or stoichiometric amount, based on the compound of the general formula (II).