15232-95-8

Upstream product

• 64-19-7 acetic acid 
• 1521-51-3 rac-3-bromocyclohexene 
• 762-72-1 allyl-trimethyl-silane 
• 822-67-3 Cyclohex-2-enol 
• 102853-22-5 cyclohex-2-en-1-yl 2,4,6-trimethylbenzoate 
• 1730-25-2 allylmagnesium bromide 

Downstream Products

• 122800-58-2 3-acetoxy-6-(2-propenyl)cyclohexene 
• 122800-57-1 3-(1-acetoxy-2-propenyl)cyclohexene 
• 1620165-81-2 methyl 5-(3-(cyclohex-2-en-1-yl)prop-1-en-2-yl)-2-methylfuran-3-carboxylate 
• 1620165-82-3 C₁₆H₂₀O₃ 
• 15745-75-2 1--propanol-3-<4-nitro-benzolsulfonat> 
• 127346-91-2 3-triphenylmethyl-5-<(2-cyclohexen-1-yl)methyl>-2-isoxazoline 
• 15745-87-6 3-cyclohex-2-en-1-ylpropan-1-ol 

Relevant academic research and scientific papers

Silver Salt-Mediated Allylation Reactions Using Allyl Bromides

A facile, efficient, and chemoselective synthesis of allylic amides has been developed. Allyl bromides were used as the precursors activated by silver triflate. A Ritter-type reaction readily proceeded to give various allyl amides under mild conditions. The reaction protocol was also applicable to different nucleophilic partners to give a wide range of allyl-substituted products in the absence of a base.

Iridium-catalyzed oxidative olefination of furans with unactivated alkenes

The oxidative coupling of arenes and alkenes is an attractive strategy for the synthesis of vinylarenes, but reactions with unactivated alkenes have typically occurred in low yield. We report an Ir-catalyzed oxidative coupling of furans with unactivated olefins to generate branched vinylfuran products in high yields and with high selectivities with a second alkene as the hydrogen acceptor. Detailed mechanistic experiments revealed catalyst decomposition pathways that were alleviated by the judicious selection of reaction conditions and application of new ligands.

High-yielding and rapid carbon-carbon bond formation from alcohols: Allylation by means of TiCl4

TiCl4 efficiently promotes high yield (80-99%) replacement of OH in tertiary, benzylic, and allylic alcohols, and even nonactivated secondary alcohols, by an allyl group. The reaction usually proceeds within minutes at room temperature. Georg Thieme Verlag Stuttgart. New York.

Fluorinated alcohols as promoters for the metal-free direct substitution reaction of allylic alcohols with nitrogenated, silylated, and carbon nucleophiles

The direct allylic substitution reaction using allylic alcohols in 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) and 2,2,2-trifluoroethanol (TFE) as reaction media is described. The developed procedure is simple, works under mild conditions (rt, 50 and 70 °C), and proves to be very general, since different nitrogenated nucleophiles and carbon nucleophiles can be used achieving high yields, especially when HFIP is employed as solvent and aromatic allylic alcohols are the substrates. Thus, sulfonamides, carbamates, carboxamides, and amines can be successfully employed as nitrogen-based nucleophiles. Likewise, silylated nucleophiles such as trimethylsilylazide, allyltrimethylsilane, trimethylsilane, and trimethylsilylphenylacetylene give the corresponding allylic substitution products in high yields. Good results for the Friedel-Crafts adducts are also achieved with aromatic compounds (phenol, anisole, indole, and anilines) as nucleophiles. Particularly interesting are the results obtained with electron-rich anilines, which can behave as nitrogenated or carbon nucleophiles depending on their electronic properties and the solvent employed. In addition, 1,3-dicarbonyl compounds (acetylacetone and Meldrum's acid) are also successfully employed as soft carbon nucleophiles. Studies for mechanism elucidation are also reported, pointing toward the existence of carbocationic intermediates and two working reaction pathways for the obtention of the allylic substitution product.

Calcium-catalyzed direct coupling of alcohols with organosilanes

A calcium-catalyzed direct substitution of π-activated alcohols with different organosilanes under very mild reaction conditions is presented. The high reactivity of the calcium catalyst allows efficient conversion of secondary and tertiary allylic, secondary benzylic, and tertiary propargylic alcohols with allyltrimethylsilane at room temperature. Furthermore, the first direct substitution of an alcohol with (E)- as well as (Z)-alkenylsilanes was achieved under mild reaction conditions. Copyright

Nucleophilic substitution reactions of alcohols with use of montmorillonite catalysts as solid Bronsted acids

(Chemical Equation Presented) We have developed an environmentally benign synthetic approach to nucleophilic substitution reactions of alcohols that minimizes or eliminates the formation of byproducts, resulting in a highly atom-efficient chemical process. Proton- and metal-exchanged montmorillonites (H- and Mn+-mont) were prepared easily by treating Na +-mont with an aqueous solution of hydrogen chloride or metal salt, respectively. The H-mont possessed outstanding catalytic activity for nucleophilic substitution reactions of a variety of alcohols with anilines, because the unique acidity of the H-mont catalyst effectively prevents the neutralization by the basic anilines. In addition, amides, indoles, 1,3-dicarbonyl compounds, and allylsilane act as nucleophiles for the H-mont-catalyzed substitutions of alcohols, which allowed efficient formation of various C-N and C-C bonds. The solid H-mont was reusable without any appreciable loss in its catalytic activity and selectivity. Especially, an Al3+-mont showed high catalytic activity for the α-benzylation of 1,3-dicarbonyl compounds with primary alcohols due to cooperative catalysis between a protonic acid site and a Lewis acidic Al3+ species in its interlayer spaces.

Direct coupling reaction between alcohols and silyl compounds: Enhancement of Lewis acidity of Me3SiBr using InCl3

The combination of InCl3 and Me3SiBr provided an enhanced Lewis acid system that can be used to promote a wide range of direct coupling reactions between alcohols and silyl nucleophiles in non-halogenated solvents, such as hexane or MeCN. The enhanced Lewis acidity of this system was measured by the 13C NMR in terms of the coordination to an alcohol. Moreover, the interaction between Me3SiBr and the In(III) species was revealed by 29Si NMR spectral analysis. Highly chemoselective allylations toward a hydroxyl moiety over ketone and acetoxy ones have been demonstrated.

Indium-silicon combined Lewis acid catalyst for direct allylation of alcohols with allyltrimethylsilane in non-halogenated solvent

A direct allylation of alcohols is effectively catalyzed by a combined Lewis acid system of InCl3 and Me3SiBr. This system allows use of non-halogenated solvents such as hexane and application to a wide range of alcohols. Georg Thieme Verlag Stuttgart.

Palladium-Catalized Oxidative Cyclization of 1,5-Dienes. Influence of Diferent Substitution Patterns on the Regio- and Stereochemistry of the Reaction

Oxidative cyclization of 1,5-dienes in acetic acid in the presence of the Pd(II) regenerating catalyst system Pd(OAc)2/MnO2/p-benzoquinone has been shown to yield, depending on the structure of the 1,5-diene, acetoxyexomethylenecyclopentanes or acetoxyvin

Alkylation of Allylic Derivatives. 11. Copper(I)-Catalyzed Cross Coupling of Allylic Carboxylates with Grignard Reagents

Reactions of allylic carboxylates with Grignard reagents containing catalytic amounts (1-10 mol percent) of cuprous salts give high yields of cross-coupled products.With alkyl Grignard reagents, regiochemistry can be controlled by choice of cuprous salt.With cuprous halides, little regiospecificity is observed.There is a small excess of γ-coupling in unbiased systems such as 5-methyl-2-cyclohexenyl (1), 2-cyclohexenyl (3), and β-phenylallyl (5) carboxylates.With CuCN, complete regiospecificity (exclusive γ-coupling) is observed with all alkyl Grignard reagents in unbiased systems, and with n-butylmagnesium halide >97percent γ-coupling results with α-methyl-γ-phenylallyl pivalate (7-OPiv) which is biased in favour of coupling at the α-position.In sharp contrast to alkyl Grignard reagents, phenyl and vinyl Grignard reagents containing CuCN show no regiospecificity.