771-73-3

Upstream product

• 1165952-91-9 cyclohexa-1,3-diene 
• 292638-85-8 acrylic acid methyl ester 
• 118751-72-7 2-methoxycarbonylbicyclo<2.2.2>octa-2,5-diene 
• 1165952-92-0 cyclohexa-1,4-diene 
• 186581-53-3 diazomethane 
• 20507-56-6 bicyclo<2.2.2>oct-5-ene-2-exo-carboxylic acid 
• 110-83-8 cyclohexene 
• 67-56-1 methanol 
• 814-68-6 acryloyl chloride 
• 40610-12-6 Bicyclo<2.2.2>oct-5-ene-2-carboxylic acid 

Downstream Products

• 40610-12-6 Bicyclo<2.2.2>oct-5-ene-2-carboxylic acid 
• 20507-56-6 bicyclo<2.2.2>oct-5-ene-2-exo-carboxylic acid 
• 771-73-3 5-exo-methoxycarbonylbicyclo<2.2.2>oct-2-ene 
• 20507-56-6 (2-endo)-bicyclo<2.2.2>oct-5-ene-2-carboxylic acid 
• 4517-47-9 endo-5-methylbicyclo<2.2.2>oct-2-ene 
• 500-23-2 bicyclo<2.2.2>-octa-2,5-diene 
• 14003-84-0 4-(2-hydroxyphenyl)-1-butene 
• 76784-85-5 trimethyl r-1,c-2,c-4-cyclohexanetricarboxylate 
• 76784-85-5 trimethyl r-1,t-2,c-4-cyclohexanetricarboxylate 

Relevant academic research and scientific papers

Norbornene based-sulfide-stabilized silylium ions: synthesis, structure and application in catalysis

A norbornene-based sulfide stabilized silylium ion 4 has been synthesized. The S–Si interaction was studied in solution and in the solid state by NMR spectroscopy and X-ray diffraction analysis as well as DFT calculations. Unlike the previously reported phosphine-stabilized silylium ion VII, behaving as a Lewis pair, calculations predict that 4 should behave as a Lewis acid toward acrylate derivatives. Indeed, the base-stabilized silylium ion 4 has emerged as an easy-to-handle silylium ion-based Lewis acid catalyst, particularly for the Diels–Alder cycloaddition, with poorly reactive dienes, and hydrodefluorination reactions.

Dehydroxymethylation of alcohols enabled by cerium photocatalysis

Dehydroxymethylation, the direct conversion of alcohol feedstocks as alkyl synthons containing one less carbon atom, is an unconventional and underexplored strategy to exploit the ubiquity and robustness of alcohol materials. Under mild and redox-neutral reaction conditions, utilizing inexpensive cerium catalyst, the photocatalytic dehydroxymethylation platform has been furnished. Enabled by ligand-to-metal charge transfer catalysis, an alcohol functionality has been reliably transferred into nucleophilic radicals with the loss of one molecule of formaldehyde. Intriguingly, we found that the dehydroxymethylation process can be significantly promoted by the cerium catalyst, and the stabilization effect of the fragmented radicals also plays a significant role. This operationally simple protocol has enabled the direct utilization of primary alcohols as unconventional alkyl nucleophiles for radical-mediated 1,4-conjugate additions with Michael acceptors. A broad range of alcohols, from simple ethanol to complex nucleosides and steroids, have been successfully applied to this fragment coupling transformation. Furthermore, the modularity of this catalytic system has been demonstrated in diversified radical-mediated transformations including hydrogenation, amination, alkenylation, and oxidation.

Dehydroxymethylation of Alcohols Enabled by Cerium Photocatalysis

Dehydroxymethylation, the direct conversion of alcohol feedstocks as alkyl synthons containing one less carbon atom, is an unconventional and underexplored strategy to exploit the ubiquity and robustness of alcohol materials. Under mild and redox-neutral reaction conditions, utilizing inexpensive cerium catalyst, the photocatalytic dehydroxymethylation platform has been furnished. Enabled by ligand-to-metal charge transfer catalysis, an alcohol functionality has been reliably transferred into nucleophilic radicals with the loss of one molecule of formaldehyde. Intriguingly, we found that the dehydroxymethylation process can be significantly promoted by the cerium catalyst, and the stabilization effect of the fragmented radicals also plays a significant role. This operationally simple protocol has enabled the direct utilization of primary alcohols as unconventional alkyl nucleophiles for radical-mediated 1,4-conjugate additions with Michael acceptors. A broad range of alcohols, from simple ethanol to complex nucleosides and steroids, have been successfully applied to this fragment coupling transformation. Furthermore, the modularity of this catalytic system has been demonstrated in diversified radical-mediated transformations including hydrogenation, amination, alkenylation, and oxidation.

Investigation of a new chiral auxiliary derived chemoenzymatically from toluene: Experimental and computational study

A tricyclic chiral auxiliary, prepared from the enzymatically derived cis-arene dihydrodiol metabolite of toluene, was investigated as a means of asymmetric induction in several different reactions. The auxiliary was converted to an oxaziridine, and its u

Synthetic studies toward polytwistane hydrocarbon nanorods

A synthetic strategy toward the intriguing hydrocarbon nanorod polytwistane is outlined. Our approach aims toward the polymerization of acetylene starting from precursors that would provide a helical bias for the formation of polytwistane. Both transition-metal-catalyzed and radical polymerizations were investigated. Two potential initiator molecules were synthesized that could be used for either approach. Although the intended regioselectivities were not observed, unusual organopalladium complexes and numerous compounds with novel carbon skeletons were obtained.

A step toward polytwistane: Synthesis and characterization of C 2-symmetric tritwistane

Twistane is a classic hydrocarbon with fascinating stereochemical properties. Herein we describe a series of oligomers of twistane that converges on a chiral nanorod, which we term polytwistane. A member of this series, C 2-symmetric tritwistane, has been synthesized for the first time. This journal is The Royal Society of Chemistry.

Silylium ion-catalyzed challenging Diels-Alder reactions: The danger of hidden proton catalysis with strong Lewis acids

The pronounced Lewis acidity of tricoordinate silicon cations brings about unusual reactivity in Lewis acid catalysis. The downside of catalysis with strong Lewis acids is, though, that these do have the potential to mediate the formation of protons by various mechanisms, and the thus released Bronsted acid might even outcompete the Lewis acid as the true catalyst. That is an often ignored point. One way of eliminating a hidden proton-catalyzed pathway is to add a proton scavenger. The low-temperature Diels-Alder reactions catalyzed by our ferrocene-stabilized silicon cation are such a case where the possibility of proton catalysis must be meticulously examined. Addition of the common hindered base 2,6-di-tert-butylpyridine resulted, however, in slow decomposition along with formation of the corresponding pyridinium ion. Quantitative deprotonation of the silicon cation was observed with more basic (Mes)3P to yield the phosphonium ion. A deuterium-labeling experiment verified that the proton is abstracted from the ferrocene backbone. A reasonable mechanism of the proton formation is proposed on the basis of quantum-chemical calculations. This is, admittedly, a particular case but suggests that the use of proton scavengers must be carefully scrutinized, as proton formation might be provoked rather than prevented. Proton-catalyzed Diels-Alder reactions are not well-documented in the literature, and a representative survey employing TfOH is included here. The outcome of these catalyses is compared with our silylium ion-catalyzed Diels-Alder reactions, thereby clearly corroborating that hidden Bronsted acid catalysis is not operating with our Lewis acid. Several simple-looking but challenging Diels-Alder reactions with exceptionally rare dienophile/enophile combinations are reported. Another indication is obtained from the chemoselectivity of the catalyses. The silylium ion-catalyzed Diels-Alder reaction is general with regard to the oxidation level of the α,β-unsaturated dienophile (carbonyl and carboxyl), whereas proton catalysis is limited to carbonyl compounds.

Taming the silylium ion for low-temperature diels-alder reactions

Some like it hot: A novel silicon-based Lewis acid having a trivalent silicon cation stabilized by an electron-rich transition metal as the "hot" Lewis acidic site catalyzes challenging Diels-Alder reactions at low temperatures with excellent reaction rat

Use of functionalized onium salts as a soluble support for organic synthesis

The invention relates to the use of a onium salt functionalized by at least one organic function, as a soluble support, in the presence of at least one organic solvent, for organic synthesis of a molecule, in a homogenous phase, by at least one transformation of said organic function. The onium salt enables the synthesized molecule to be released. The onium salt is present in liquid or solid form at room temperature and corresponds to formula A1+, X1?, wherein A1+ represents a cation and X1? represents an anion.

Hybrid bidentate ligand for functional recognition: An application to regioselective C=C double bond hydrogenation

Regioselectivity increases in C=C double bond hydrogenation could be obtained for Lewis basic substrates on a Lewis acidic support by using a rhodium complex supported on a mesoporous solid. The Royal Society of Chemistry 2006.