140198-41-0

Upstream product

• 563-52-0 2-chloro-3-butene 
• 13139-86-1 4-methoxyphenyl magnesium bromide 
• 696-62-8 para-iodoanisole 
• 623-12-1 4-chloromethoxybenzene 
• 97370-29-1 (3R,4R)-2,2,3,4-tetramethyl-5-hexene-3-ol 
• 85312-77-2 2,2,3,4-tetramethyl-5-hexen-3-ol 
• 2746-25-0 p-Methoxybenzyl bromide 
• 35191-43-6 1-(4-bromo-butyl)-4-methoxy-benzene 
• 1106964-40-2 1-methylprop-2-ene-1-sulfonyl chloride 
• 459-64-3 4-methoxybenzenediazonium tetrafluoroborate 
• 20574-98-5 4-(p-methoxyphenyl)but-1-ene 
• 591-97-9 1-chloro-2-butene 

Relevant academic research and scientific papers

Solvolytic Stereoselective Coupling of p-Methoxyphenylmagnesium Bromide with Substituted Allylic Chlorides

The α- and γ-coupling reactions of a few substituted allylic chlorides with p-methoxyphenylmagnesium bromide were concluded as to involve the formation of an intimate ion-pair intermediate.The solvents used gave substantial effects both on the regio-and stereo-selectivity of the reaction.

Functionalized arylzinc compounds in ethereal solvent: Direct synthesis from aryl iodides and zinc powder and application to Pd-catalyzed reaction with allylic halides

Arylzinc compounds, ArZnX, were conveniently prepared in high yields by the reaction of zinc powder with aryl iodides, which contain electron-withdrawing groups such as CO2CH3, CN, Br, or CF3 at the ortho-, meta- or para-position, or electron-donating groups such as CH3, OCH3, or H, at 70 °C in THF, at 100 °C, or at 130 °C in diglyme, respectively. Pd(dba)2 exhibited an outstanding efficient catalytic effect for the cross-coupling of these ethereal solutions of ArZnX with allylic halides to afford a variety of functionalized allylbenzenes in high yields; the reactions were mostly carried out at 0 °C for 5-30 min in the presence of 5 mol % of catalyst. The conversion of the aryl iodides to allylbenzenes via two reactions could be accomplished in one pot.

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.

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.

Allylation and vinylation of aryl radicals generated from diazonium salts

(Chemical Equation Presented) Allylation and vinylation of aryl radicals generated from aryl diazonium salts provides rapid and efficient access to chlorinated and brominated derivatives of styrene and allylbenzene. Allyl chlorides were found to be better substrates than bromides due to decreased halogen transfer. Donor- and acceptor-substituted diazonium salts are well tolerated. The products represent important precursors for numerous further transformations.

Pd(OAc)2/P(cC6H11) 3-catalyzed allylation of aryl halides with homoallyl alcohols via retro-allylation

Allylations of aryl halides take place upon treatment of tertiary homoallyl alcohols with aryl halides in the presence of cesium carbonate and a palladium catalyst. The allylation reaction would consist of the following steps: (1) oxidative addition of ar

Development of isomerization and cycloisomerization with use of a ruthenium hydride with N-heterocyclic carbene and its application to the synthesis of heterocycles

A pure ruthenium hydride complex with N-heterocyclic carbene (NHC) ligand was efficiently generated from the reaction of a second-generation Grubbs ruthenium catalyst with vinyloxytrimethylsilane and unambiguously characterized. This ruthenium hydride complex showed high catalytic activity for the selective isomerization of terminal olefin and for the cycloisomerization of 1,6-dienes. These reactions of N-allyl-o-vinylaniline lead to novel synthetic methods for heterocycles such as indoles and 3-methylene-2,3-dihydroindoles, which are useful synthons for bioactive natural products. These procedures address an important issue in diversity-oriented synthesis.