25694-29-5

Upstream product

• 1165952-91-9 cyclohexa-1,3-diene 
• 292638-85-8 acrylic acid methyl ester 
• 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 
• 771-73-3 5-methoxycarbonylbicyclo<2.2.2>oct-2-ene 
• 40610-12-6 Bicyclo<2.2.2>oct-5-ene-2-carboxylic acid 

Downstream Products

• 20507-56-6 (2-endo)-bicyclo<2.2.2>oct-5-ene-2-carboxylic acid 
• 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 
• 4517-47-9 endo-5-methylbicyclo<2.2.2>oct-2-ene 

Relevant academic research and scientific papers

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.

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.

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.

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

Strong counteranion effects on the catalytic activity of cationic silicon lewis acids in Mukaiyama aldol and Diels-Alder reactions

(Graph Presented) A toluene-coordinated silyl borate, [Et 3Si(toluene)]B(C6F5)4, demonstrated catalytic activities significantly higher than those of Me3SiOTf and Me3SiNTf2 in Mu

Fructose-derived ionic liquids: Recyclable homogeneous supports

A new homogeneous support has been developed that is based on a fructose-derived ionic liquid. It has been applied to the preparation of a series of supported Diels-Alder adducts. The cleavage of these adducts from the ionic liquid has resulted in some interesting observations regarding the base stability of imidazolium cations. Using a transesterification cleavage, the ionic support can be recovered and recycled.

Trimethylsilyl bis(trifluoromethanesulfonyl)imide as a tolerant and environmentally benign Lewis acid catalyst of the Diels-Alder reaction

N-trimethylsilyl bis(trifluoromethanesulfonyl)imide (TMSNTf2) was readily prepared in situ by protodesilylation of trimethylsilane, allyl- or phenyltrimethylsilane with bis(trifluoromethylsulfonyl)imide. NMR studies showed that TMSNTf2 was much more effective than TMSOTf in complexing the carbonyl group of trans-methylcrotonate. As a result, TMSNTf2 was found to be superior to TMSOTf as a catalyst for the Diels-Alder reaction of α,β-unsaturated esters with a wide variety of dienes. In contrast to many metal derived Lewis acids, TMSNTf2 was found tolerant of many sensitive functional groups present in the diene partner.

Orbital unsymmetrization of olefins arising from non-equivalent orbital interactions. σ-π Coupling in bicyclo[2.2.2]octenes

We characterized experimentally the substituent effect of a 5-exo substituent on the π facial selectivities of bicyclo[2.2.2]octenes toward electrophilic oxidative reactions such as epoxidation and dihydroxylation, and we discuss the underlying orbital interactions of vicinal σ orbitals and the olefinic π orbital involved in bicyclo[2.2.2]octenes, and commonly in methylenenorbornanes. Of significance is the out-of-phase motif of these σ- π couplings. Electron-withdrawing substituents such as cyano and carboxylic acid groups unequalize the relevant σ-π coupling, leading to the observed syn-facial preference. Alkyl substituents exhibit an electron-donative perturbing effect, depending on the bicyclic ring system.