21003-53-2

Upstream product

• 124745-26-2 4-<(1-methyl-3-(4-methylphenyl)prop-2-enyl)sulfinyl>morpholine 
• 106-99-0 buta-1,3-diene 
• 4294-57-9 para-methylphenylmagnesium bromide 
• 86739-16-4 <((E)-But-2-enyl)oxy>trimethylsilan 
• 563-52-0 2-chloro-3-butene 
• 108-88-3 toluene 
• 4894-61-5 trans-but-2-enyl chloride 
• 4784-77-4 (E)-1-Bromo-2-butene 
• 5720-05-8 4-methylphenylboronic acid 
• 20574-99-6 1-(but-3-en-1-yl)-4-methylbenzene 
• 104-81-4 4-Methylbenzyl bromide 
• 90252-89-4 p-tolylzinc(II) chloride 
• 1106964-40-2 1-methylprop-2-ene-1-sulfonyl chloride 

Downstream Products

• 94739-52-3 3-methyl-1-p-tolylbutan-2-one 

Relevant academic research and scientific papers

METHODS OF BORYLATION AND USES THEREOF

The present invention relates, in general terms, to methods of borylation and uses thereof. In particular, the present invention provides a method of borylating an alkene compound by contacting the compound with a boron compound, a Fe pre-catalyst and a protic additive. The borylation occurs at a vicinal (β) position to an electron donating or electron withdrawing moiety of the compound.

Iron-Catalyzed Tunable and Site-Selective Olefin Transposition

The catalytic isomerization of C-C double bonds is an indispensable chemical transformation used to deliver higher-value analogues and has important utility in the chemical industry. Notwithstanding the advances reported in this field, there is compelling demand for a general catalytic solution that enables precise control of the C═C bond migration position, in both cyclic and acyclic systems, to furnish disubstituted and trisubstituted alkenes. Here, we show that catalytic amounts of an appropriate earth-abundant iron-based complex, a base and a boryl compound, promote efficient and controllable alkene transposition. Mechanistic investigations reveal that these processes likely involve in situ formation of an iron-hydride species which promotes olefin isomerization through sequential olefin insertion/β-hydride elimination. Through this strategy, regiodivergent access to different products from one substrate can be facilitated, isomeric olefin mixtures commonly found in petroleum-derived feedstock can be transformed to a single alkene product, and unsaturated moieties embedded within linear and heterocyclic biologically active entities can be obtained.

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.

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

Ligandless iron-catalyzed desulfinylative C-C allylation reactions using Grignard reagents and alk-2-enesulfonyl chlorides

Alk-2-enesulfonyl chlorides 1-4 were synthesized by the BCl3-promoted ene reaction of alkenes with SO2. These sulfonyl chlorides were then used as electrophilic partners in iron-catalyzed desulfinylative cross-coupling reactions with different Grignard reagents (aromatic, aliphatic, and heteroaromatic). The reaction can be catalyzed with even 2 mol-% of the simple iron salt Fe(acac)3. The regioselectivity of these allylations was studied by using sulfonyl chlorides 3 and 4 with aryl Grignard reagents. The scope of these allylations was further extended by the coupling of ester-substituted alk-2-enesulfonyl chloride 10 with aromatic Grignard reagents. Symmetrical products were synthesized by double C-C allylation with the use of 2-methylidenepropane-1,3-disulfonyl chloride (12). Wiley-VCH Verlag GmbH & Co. KGaA.

Hydrogen peroxide-or sodium hypochlorite-induced bromination of 1-arylbut-2-enes

Bromination of 1-arylbut-2-enes in the system [HBr or NaBr (KBr)-HX]-H 2O2 (or NaOCl) under relatively mild conditions leads to electrophilic addition of bromine or hypobromous acid at the side-chain double bond. Under more severe conditions, the process is accompanied by bromination of the aromatic ring. Treatment of the title compounds with peroxy acids (RCOOH-H2O2) gives the corresponding epoxy derivatives which react with HBr and oxygen-containing nucleophiles to produce α-bromo alcohols, diols, and diol acetates.

Solventless Suzuki coupling reactions on palladium-doped potassium fluoride alumina

A solventless Suzuki coupling reaction has been developed which utilizes a commercially available potassium fluoride alumina mixture and palladium powder. The new reaction is convenient, environmentally friendly, and generates good yields of the coupled products. Aryl iodides react faster than the bromides or chlorides; aryl groups are also more reactive than alkenyl groups, which react faster than alkyl groups. The use of microwave irradiation accelerates the reaction, decreasing reaction times from hours to minutes. The palladium powder catalyst can be recycled using a simple filtration and washing sequence without loss of catalytic activity.

A new direct allylation of the aromatic compounds with allylic chlorides catalyzed by indium metal

A new method of the direct allylation reaction for the aromatic compounds with allylic chlorides using a catalytic mount of indium in the presence of CaCO3/4A molecular sieves was developed.

Detailed Characterization of p-Toluenesulfonic Acid Monohydrate as a Convenient, Recoverable, Safe, and Selective Catalyst for Alkylation of the Aromatic Nucleus

Alkylation of the aromatic nucleus, an important reaction in industry and synthetic organic chemistry, has traditionally been carried out by the well-known Friedel-Crafts reaction employing Lewis acid catalysts such as AlCl3 and BF3 or by using highly reactive organometallic reagents. Although protic acids such as anhydrous HF and concentrated H2SO4 have also been used in the alkylation of the aromatic nucleus, the notoriously corrosive, highly toxic, and hazardous nature of these agents has precluded their common use under ordinary laboratory conditions. Various organic sulfonic acids have, on occasion, been used as catalysts in Friedel-Crafts alkylations, but to our knowledge the chemistry and the scope of these reactions for common laboratory use have never been exploited in detail. In the present study we have characterized commercially available p-toluenesulfonic acid monohydrate (TsOH) as an efficient catalyst for the intermolecular coupling of the aromatic nucleus with activated alkyl halides, alkenes, or tosylates under mild conditions in an open atmosphere. In comparison to conventional Friedel-Crafts catalysts such as AlCl3, BF3, HF, and concentrated H2SO4, the extent of the formation of undesired products from side reactions such as transalkylation, polymerization, etc. was minimal with the TsOH-catalyzed reaction. The ability to recover and reuse the catalyst from the reaction mixtures, minimal generation of environmentally unfriendly waste, high specificity of the reaction, and the low cost of the catalyst are important advantages of the TsOH catalyst over the other conventional Friedel-Crafts catalysts.