62121-84-0

Upstream product

• 4982-34-7 1,4-diphenyl-1,3-cyclopentadiene 

Downstream Products

• 87051-11-4 (4aS,7aS)-3-Methyl-6,7a-diphenyl-7,7a-dihydro-4aH-cyclopenta[1,2,4]trioxine 
• 87051-12-5 (4aRS,7aRS)-4a,7a-dihydro-3,3-dimethyl-6,7a-diphenyl-7H-cyclopenta<1,2-e><1,2,4>trioxine 
• 4982-34-7 1,4-diphenyl-1,3-cyclopentadiene 
• 124378-33-2 (4'aS,7'aS)-4'a,7'a-dihydro-6',7'a-diphenylspiro<1,2,4>trioxine> 
• 145909-94-0 (3aR,5aS,8aS,8bS)-2,5a,7,8b-Tetraphenyl-5a,6,8a,8b-tetrahydro-3aH-cyclopenta[c]furo[2,3-e][1,2]dioxine 
• 139054-32-3 (1R,2S,4'aS,5R,7'aS)-4'a,7'-dihydro-6,6-dimethyl-6',7'a-diphenylspiro(bicyclo[3.1,1]heptane-2,3'-[7H]cyclopenta[1,2,4]trioxine) 
• 139164-11-7 (1R,2R,3'aS,5S,6'aR)-3'a,6'a-dihydro-6,6-dimethyl-3'a-phenoxy-5'-phenylspiro(bicyclo[3.1.1]heptane-2,2'-[4H]cyclopenta[1,3]dioxole) 
• 139054-33-4 (1R,2S,3'aR,5S,6'aS)-3'a,6'a-dihydro-6,6-dimethyl-3'a-phenoxy-5'-phenylspiro(bicyclo[3.1.1]heptane-2,2'-[4H]cyclopenta[1,3]dioxole) 
• 145909-93-9 cis,cis-3a,5a,8a,8b-tetrahydro-2,5a,7,8b-tetraphenyl-1H,6H-dicyclopenta-1,2-dioxine 
• 1192037-41-4 exo-1,5-diphenyl-6,7-dioxatricyclo[3.2.1.0(2,4)]octane 

Relevant academic research and scientific papers

Cis-fused dihydrofurano-1,2,4-trioxanes

The endoperoxide obtained from 2,5-diphenylfuran at -30°C on catalysis with trimethylsilyl trifluoromethanesulfonate condenses with pivalaldehyde, acetone and cyclohexanone to give the corresponding cis-fused dihydrofurano-1,2,4-trioxanes (20, 21, 22 and

Dissociative electron transfer to diphenyl-substituted bicyclic endoperoxides: The effect of molecular structure on the reactivity of distonic radical anions and determination of thermochemical parameters

The heterogeneous electron transfer reduction of the bicyclic endoperoxide 1,4-diphenyl-2,3-dioxabicyclo[2.2.1]hept-5-ene (4) was investigated in N,N-dimethylformamide at a glassy carbon electrode. The endoperoxide reacts by a concerted dissociative ET me

Palladium-catalyzed cyclopropanation of unsaturated endoperoxides. A new peroxide-preserving reaction

Unsaturated bicyclic endoperoxides are efficiently cyclopropanated with excess diazomethane in the presence of catalytic palladium(II) acetate [Pd(OAc)2] in a stereoselective manner. This method represents a new peroxide-preserving transformati

A radical-anion chain mechanism following dissociative electron transfer reduction of the model prostaglandin endoperoxide, 1,4-diphenyl-2,3- dioxabicyclo[2.2.1]heptane

The model prostaglandin endoperoxide, 1,4-diphenyl-2,3-dioxabicyclo[2.2.1] heptane (3), was investigated in N,N-dimethylformamide at a glassy carbon electrode using various electrochemical techniques. Reduction of 3 occurs by a concerted dissociative electron transfer (ET) mechanism. Electrolysis at -1.6 V yields 1,3-diphenyl-cyclopentane-cis-1,3-diol in 97% by a two-electron mechanism; however, in competition with the second ET from the electrode, the resulting distonic radical-anion intermediate undergoes a β-scission fragmentation. The rate constant for the heterogeneous ET to the distonic radical-anion is estimated to occur on the order of 2 × 107 s-1. In contrast, electrolyses conducted at potentials more negative than -2.1 V yield a mixture of primary and secondary electrolysis products including 1,3-diphenyl-cyclopentane-cis-1,3-diol, 1,3-diphenyl-1,3-propanedione, trans-chalcone and 1,3-diphenyl-1,3-hydroxypropane by a mechanism involving less than one electron equivalent. These observations are rationalized by a catalytic radical-anion chain mechanism, which is dependent on the electrode potential and the concentration of weak non-nucleophilic acid. A thermochemical cycle for calculating the driving force for β-scission fragmentation from oxygen-centred biradicals and analogous distonic radical-anions is presented and the results of the calculations provide insight into the reactivity of prostaglandin endoperoxides.

Extreme rate acceleration by axial thiolate coordination on the isomerization of endoperoxide catalyzed by iron porphyrin

(Chemical Equation Presented) A coordinated effort: The isomerization mechanism of prostaglandin H2 (PGH2), which is catalytically isomerized to prostacyclin or thromboxane A2 by cytochrome P450s, was investigated using a hemethiolate complex and an endoperoxide. Isomerization of endoperoxides proceeded very rapidly with this complex, whereas imidazole- or chloride-ligated heme had slight or no catalytic activity (see scheme).

Lewis acid catalysed rearrangements of unsaturated bicyclic [2.2.n] endoperoxides in the presence of vinyl silanes; access to novel Fenozan BO-7 analogues

Reactions of a series of unsaturated bicyclic [2.2.n] endoperoxides with allyltrimethylsilane in the presence TMSOTf or SnCl4 provides the cis-configured endoperoxides 9a-12. It is proposed that this novel reaction proceeds via attack of the al

Synthesis and Antimalarial Activity of Trioxaquine Derivatives

Trioxaquines are dual molecules that contain a trioxane motif linked to an aminoquinoline entity. Among the different compounds of this series, trioxaquine cis-15 (DU1302c), prepared from α-terpinene, a cheap natural product, showed efficient antimalarial activity in vitro on both sensitive and resistant strains of Plasmodium falciparum (IC50 = 5-19 nM). A stereochemical description of this stable, nontoxic, and non-genotoxic antimalarial agent is detailed. Mice infected with P. vinckei were successfully treated with cis-15 in a four-day suppressive test. The doses required to decrease parasitemia by 50% (ED50) were 5 and 18 mg kg -1d-1 after intraperitoneal and oral administration, respectively. Parasitemia clearance was complete without recrudescence at an intraperitoneal dose of 20 mgkg-1d-1.

The Diastereoselective Formation of 1,2,4-Trioxanes and 1,3-Dioxolanes by the Reaction of Endoperoxides with Chiral Cyclohexanones

1,4-Diphenyl-2,3-dioxabicyclo[2.2.1]hept-5-ene (2), on treatment with a catalytic amount of trimethylsilyl trifluoromethanesulfonate (Me3SiOTf) in CH2Cl2 at -78°, reacts with excess (-)-menthone (10) to give (1S,2S,4′aS,5R,7′aS)-4′a,7′a-dihydro-2-isopropyl-5- methyl-6′,7′-diphenylspiro[cyclohexane-1,3′-[7′H] cyclopenta-[1,2,4]trioxine] (11) and its (1R,2S,4′aS,5R,7′aS)-diastereoisomer 12 in a 1:1 ratio and in 21% yield. Repeating the reaction with 1.1 equiv, of Me3SiOTf with respect to 2 affords 11, 12, and (1S,2S,3′aR,5R,6′aS)-3′a,6′a-dihydro-2-isopropyl-5- methyl-3′a-phenoxy-5′-phenylspiro[cyclohexane-1,2′-[4′H] cyclopenta[1,3]dioxole] (13) together with its (1R,2S,3′aS,5R,6′aR)-diastereoisomer 14 in a ratio of 3:3:3:1 and in 56% yield. (+)-Nopinone (15) in excess reacts with 2 in the presence of 1.1 equiv. of Me3SiOTf to give a pair of 1,2,4-trioxanes (16 and 17) analogous to 11 and 12, and a pair of 1,3-dioxolanes (18 and 19) analogous to 13 and 14, in a ratio of 8:2:3:3 and in 85% yield. (-)-Carvone and racemic 2-(tert-butyl)cyclohexanone under the same conditions behave like 15 and deliver pairs of diastereoisomeric trioxanes and dioxolanes. In general, catalytic amounts of Me3SiOTf give rise to trioxanes, whereas 1.5 equiv. overwhelmingly engender dioxolanes. Adamantan-2-one combines with 2 giving only (4′aRS,7′aRS)-4′a,7′a-dihydro-6′,7′a- diphenylspiro[adamantane-2,3′-[7′H]cyclopenta[1,2,4]trioxine] in 98% yield regardless of the amount of Me3SiOTf used. The reaction of 1,4-diphenyl-2,3-dioxabicyclo[2.2.2]oct-5-ene (32) with 10 and 1.1 equiv. of Me3SiOTf produces only the pair of trioxanes 33 and 34 homologous to 11 and 12. Treatment of the (S,S)-diastereoisomer 33 with Zn and AcOH furnishes (1S,2S)-1,4-diphenylcyclohex-3-ene-1,2-diol. The crystal structures of 11-13 and 16 are obtained by X-ray analysis. The reaction courses of 10 and the other chiral cyclohexanones with prochiral endoperoxides 2 and 32 to give trioxanes are rationalized in terms of the respective enantiomeric silylperoxy cations which are completely differentiated by the si and re faces of the ketone function. The origin of the 1,3-dioxolanes is ascribed to 1,2 rearrangement of the corresponding trioxanes, which occurs with retention of configuration of the angular substituent.

Synthesis, structure, and antimalarial activity of some enantiomerically pure, cis-fused cyclopenteno-1,2,4-trioxanes

Two pairs of enantiomerically pure cis-fused cyclopenteno-1,2,4-trioxanes (7, ent-7 and 8, ent-8) are prepared. Their identities are established by dye-sensitized photo-oxygenation of ent-7 and 8 to the allylic hydroperoxides, reduction to the corresponding alcohols, and conversion to the (1S)-camphanoates, the structures of which are determined by X-ray analysis. The dynamic properties of ent-7 are investigated by NMR spectroscopy and PM3 calculations. Evidence for an easily accessible twist-boat conformation is obtained. The in vitro and in vivo antimalarial activities of 7, ent-7, 8, and ent-8 as well as those of the racemic mixtures are evaluated against Plasmodium falciparum, P. berghei, and P. yoelii. No correlation is observed between configuration and activity. Racemates and pure enantiomers have commensurate activities. The mode of action on the intraerythrocytic parasite is rationalized in terms of close docking by the twist-boat conformer of the trioxane on the surface of a molecule of heme, single-electron transfer to the O-O σ* orbital, and scission to the acetal radical which then irreversibly isomerizes to a C-centered radical, the ultimate lethal agent.