Cyclopentane Dimethyl ether

Rhodium(II) acetate catalyzes C—H insertion, olefin addition, heteroatom-H insertion, and ylide formation of a-diazocarbonyls via a rhodium carbenoid species (144—147). Intramolecular cyclopentane formation via C—H insertion occurs with retention of stereochemistry (143). Chiral rhodium (TT) carboxamides catalyze enantioselective cyclopropanation and intramolecular C—N insertions of CC-diazoketones (148). Other reactions catalyzed by rhodium complexes include double-bond migration (140), hydrogenation of aromatic aldehydes and ketones to hydrocarbons (150), homologation of esters (151), carbonylation of formaldehyde (152) and amines (140), reductive carbonylation of dimethyl ether or methyl acetate to 1,1-diacetoxy ethane (153), decarbonylation of aldehydes (140), water gas shift reaction (69,154), C—C skeletal rearrangements (132,140), oxidation of olefins to ketones (155) and aldehydes (156), and oxidation of substituted anthracenes to anthraquinones (157). Rhodium-catalyzed hydrosilation of olefins, alkynes, carbonyls, alcohols, and imines is facile and may also be accomplished enantioselectively (140). Rhodium complexes are moderately active alkene and alkyne polymerization catalysts (140). In some cases polymer-supported versions of homogeneous rhodium catalysts have improved activity, compared to their homogenous counterparts. This is the case for the conversion of alkenes direcdy to alcohols under oxo conditions by rhodium—amine polymer catalysts... 

Also used as a spectral comparison model for the elucidation of the B and G aflato-xinsss this compound was prepared in a multi-step synthesis. The von Pechmann condensation of phloroglucinol dimethyl ether (59)133 with diethyl cyclopentane-4,5-dione-l, 3-dicarboxylate (41) in acidic solution afforded the /J-ketoester (42), which readily underwent decarboalkoxylation, in a seperate step, to give the keto-coumarin (5). The beauty of this methodology is illustrated by the use of the symmetrical diketoester (41), which of course, only allows for the formation of a single coumarin (von Pechmann) product (42). The regiochemistry of the final product, however, was demonstrated to be the incorrect isomer insofar as the aflatoxin structures were concerned. 

Relative values, however, should ideally reflect conformational energies. If all atom and bond types are the same, as in cyclohexane and methyl-cyclopentane, the energy functions have the same zero point, and relative stabilities can be directly compared. This is a rather special situation, however, and stabilities of different molecules can normally not be calculated by force fleld techniques. For comparing relative stabilities of chemically different molecules such as dimethyl ether and ethyl alcohol, or for comparing with experimental heat of formations, the zero point of the energy scale must be the same. 

Dimethyl cyclopentane 2,2-Dimethyl-1,3-dioxolane-4-methanol Dimethyl ether 2,6-Dimethyl heptanol-4 1,2-Dimethyl imidazole Dimethyl methylphosphonate 2,3-Dimethyl pentane 2,4-Dimethylpentane 3,3-Dimethyl pentane 2,2-Dimethylpropanol Dinonyl phenol Dioctyl adipate Dioctyl phosphite Dioctyl sebacate Diphenyl carbonate... 

Ojima has reported a rhodium-catalyzed protocol for the disilylative cyclization of diynes with hydrosilanes to form alkylidene cyclopentanes and/or cyclopentenes. As an example, reaction of dipropargylhexylamine with triethyl-silane catalyzed by Rh(acac)(GO)2 under an atmosphere of CO at 65 °G for 10 h gave an 83 17 mixture of the disilylated alkylidene pyrrolidine derivative 92b (X = N-//-hexyl) and the disilylated dihydro-1/ -pyrrole 92c (X = N-//-hexyl) in 76% combined yield (Equation (60)). Compounds 92b and 92c were presumably formed via hydrosilyla-tion and hydrosilylation/isomerization, respectively, of the initially formed silylated dialkylidene cyclopentane 92a (Equation (60)). The 92b 92c ratio was substrate dependent. Rhodium-catalyzed disilylative cyclization of dipro-pargyl ether formed the disilylated alkylidene tetrahydrofuran 92b (X = O) as the exclusive product in low yield, whereas the reaction of dimethyl dipropargylmalonate formed cyclopentene 92c [X = C(C02Et)2] as the exclusive product in 74% isolated yield (Equation (60)). 

Bornane monoterpenes are exemplified by camphene (2,2-dimethyl-3-methylene-bicyclo[2,2,1]heptane), a structure in which two fused cyclopentane rings share three Cs. We can simply represent the camphene skeleton as a cyclohexane with a methylene (—CH2—) cross-link (G6(-CH2—)). The keto derivative camphor (camphor smell), the ether eucalyptol (eucalyptus smell) and the simple bornene a-pinene (pine smell) are familiar examples. 

Cyclopentan l-Brom-2-tert.-butyl-peroxy- E13/1, 397 (HgBr -> Br) 1,3-Dioxan 2-(4-Brom-butyl)-5,5-dimethyl- E14a/1, 370 (Enol-ether 4- R—OH)... 

Simple organic compounds o-tcrphenyl, toluene, 3-mcthyl hexane, 2,3-dimethyl ketone, diethyl ether, isobutyl bromide, ethylene glycol, methyl alcohol, ethyl alcohol, glycerol, glucose. As droplets only m-xylene, cyclopentane, n-heptane, methylene chloride. 

Acetic anhydride Acrolein Aluminum chloride anhydrous 2-Aminopentane p-Anisic acid p-Anisic acid Bis (chloromethyl) ether Cetethyidimonium bromide Cetrimonium bromide Cetylpyridinium bromide Cobalt chloride (ous) Cyclohexane Cyclopentane Diacetone alcohol Dimethyl sulfate... 

As an example of the use of this methodology in total synthesis, the zirconocene-promoted ring contraction was the key step in the route to (+)-epiafricanol (100) reported by Paquette et al. [78]. Vinyl pyranose 95, obtained from D-glucose in 12 steps, was treated with Cp2Zr in toluene at -78°C and then with boron trifluoride etherate at room temperature, affording vinyl cyclopentane 96 in a 63% yield. Conversion of 96 to ketone 97 with periodinane as the oxidant in the presence of sodium bicarbonate and addition of the lithium derivative to 4,4-dimethyl-5-iodo-l-pentene 98 gave rise to 99. Cyclization of 99 by RCM followed by cyclopropanation finally afforded the desired product 100 (Scheme 3.39). 

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