18272-83-8

Upstream product

• 100-66-3 methoxybenzene 
• 121197-99-7 crotyl tripropyl pyrophosphate 
• 121197-89-5 P₁,P₂-dicrotyl P₁,P₂-dipropyl pyrophosphate 
• 104-92-7 1-bromo-4-methoxy-benzene 
• 628-08-0 crotyl acetate 
• 696-62-8 para-iodoanisole 
• 563-52-0 2-chloro-3-butene 
• 591-97-9 1-chloro-2-butene 
• 6737-11-7 2-acetoxy-3-butene 
• 1327162-50-4 sodium (Z)-2-buten-1-yl-diethylsilanolate 
• 4894-61-5 trans-but-2-enyl chloride 
• 950846-24-9 n-butylphenylzinc 
• 13139-86-1 4-methoxyphenyl magnesium bromide 
• 93296-09-4 4-methoxyphenylzinc chloride 

Downstream Products

• 140-11-4 Benzyl acetate 
• 6316-54-7 4-methoxy-benzoic acid benzyl ester 
• 4917-90-2 1-sec-butyl-4-methoxybenzene 

Relevant academic research and scientific papers

Synthesis of 3-aryl-1-butenes by the nickel catalyzed hydrovinylation of styrene derivatives

The synthesis of 3-aryl-1-butenes is performed by hydrovinylation of styrene and alkyl-substituted styrenes catalyzed by [Ni(MeCN)6][BF4]2/Et2AlCl/PPh3 under mild conditions with very good activities

B(C6F5)3-Catalyzed Ring Opening and Isomerization of Unactivated Cyclopropanes

Catalytic amounts of B(C6F5)3 promote the ring opening and subsequent isomerization of a series of unactivated cyclopropanes to afford terminal olefins in good yields when a hydrosilane and 2,6-dibromopyridine are employed as additives.

Palladium-Catalyzed Oxidative Borylation of Allylic C-H Bonds in Alkenes

This communication describes an efficient palladium pincer complex-catalyzed allylic C-H borylation of alkenes. The transformation exhibits high regio- and stereoselectivity with a variety of linear alkenes. A synthetically useful feature of this allylic C-H borylation method is that all allyl-Bpin products can be isolated in usually high yields. Preliminary mechanistic studies indicate that this C-H borylation reaction proceeds via Pd(IV) pincer complex intermediates.

Copper(I)-Catalyzed Allylic Substitutions with a Hydride Nucleophile

An easily accessible copper(I)/N-heterocyclic carbene (NHC) complex enables a regioselective hydride transfer to allylic bromides, an allylic reduction. The resulting aryl- and alkyl-substituted branched α-olefins, which are valuable building blocks for synthesis, are obtained in good yields and regioselectivity. A commercially available silane, (TMSO)2Si(Me)H, is employed as hydride source. This protocol offers a unified alternative to the established metal-catalyzed allylic substitutions with carbon nucleophiles, as no adaption of the catalyst to the nature of the nucleophile is required.

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.

Triarylphosphine ligands with hemilabile alkoxy groups: Ligands for nickel(II)-catalyzed olefin dimerization reactions. hydrovinylation of vinylarenes, 1,3-dienes, and cycloisomerization of 1,6-dienes

Substitution of one of the phenyl groups of triphenylphosphine with a 2-benzyloxy-, 2-benzyloxymethyl- or 2-benzyloxyethyl-phenyl moiety results in a set of simple ligands, which exhibit strikingly different behaviour in various nickel(II)-catalyzed olefin dimerization reactions. Complexes of ligands with 2-benzyloxyphenyl- and 2-benzyloxymethylphenyldiphenylphosphine (L5 and L6, respectively) are most active for hydrovinylation (HV) of vinylarenes, with the former leading to extensive isomerization of the primary 3-aryl-1-butenes into the conjugated 2-aryl-2-butenes even at -55 °C. However, 2-benzyloxymethyl-substituted ligand L6 is slightly less active, affording up to quantitative yields of the primary products of HV at ambient temperature with no trace of isomerization, thus providing the best option for a practical synthesis of these compounds. In sharp contrast, hydrovinylation of a variety of 1,3-dienes is best catalyzed by nickel(II) complexes of 2- benzyloxyphenyldiphenylphosphine, L5. The other two ligands, 2-benzyloxymethyl- (L6) and 2-benzyloxyethyldiphenylphosphine (L7) are much less effective in the HV of 1,3-dienes. Nickel(II)-catalyzed cycloisomerization of 1,6-dienes into methylenecyclopentanes, a reaction mechanistically related to the other hydrovinylation reactions, is also uniquely effected by nickel(II) complexes of L5, but not of L6 or L7. In an attempt to prepare authentic samples of the methylencyclohexane products, nickel(II) complexes of N-heterocyclic carbene ligands were examined. In sharp contrast to the phosphines, which give the methylenecyclopentanes, methylenecyclohexanes are the major products in the (N-heterocyclic carbene)nickel(II)-mediated reactions.

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

Enantioselective hydrovinylation via asymmetric counteranion-directed ruthenium catalysis

The first Ru-catalyzed enantioselective hydrovinylation has been realized by using an asymmetric counteranion-directed catalysis strategy. Styrene derivatives react with ethylene in excellent yields and promising enantioselectivity using this approach. Th

γ-Selective cross-coupling of allylic silanolate salts with aromatic bromides using trialkylphosphonium tetrafluoroborate salts prepared directly from phosphine?borane adducts

The γ-selective, palladium-catalyzed cross-coupling of sodium (Z)-2-butenyldiethylsilanolate with a variety of aromatic bromides is reported. The protocol provides high yields (73-94%) and site selectivity (γ/α, 25:1 → > 99:1) in the coupling of electron-

Practical iron-catalyzed allylations of aryl grignard reagents

An operationally simple iron-catalyzed reductive cross-coupling reaction between aryl halides and allyl electrophiles has been developed. The underlying domino process exhibits high versatility with respect to the allylic leaving group (acetate, tosylate, diethyl phosphate, methyl carbonate, trimethylsilanolate, methanethiolate, chloride, bromide) and high economic and environmental sustainability with respect to the catalyst system (0.2-5 mol% tris(acetylacetonato)iron(III), ligand-free) and reaction conditions (tetrahydrofuran, 0°C, 45 min).