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Full-Text Articles in Physical Sciences and Mathematics
Recent Applications Of The Simple Hydrocarbon Cyclooctatetrene As A Starting Material For Complex Molecule Synthesis, Kevin W. Glaeske, William Donaldson
Recent Applications Of The Simple Hydrocarbon Cyclooctatetrene As A Starting Material For Complex Molecule Synthesis, Kevin W. Glaeske, William Donaldson
Chemistry Faculty Research and Publications
Cyclooctatetraene [COT], a simple non-aromatic cyclic polyene, is capable of undergoing a variety of oxidation and cycloaddition reactions to afford polycyclic structures. In addition, complexation of COT or the cycloaddition products with transition metals facilitates bond formation. Recent developments in the reactivity of COT and application to the synthesis of naturally occurring and non-naturally occurring compounds is reviewed.
Reactivity Of Acyclic (Pentadienyl)Iron(1+) Cations: Synthetic Studies Directed Toward The Frondosins, Do W. Lee, Rajesh K. Pandey, Sergey Lindeman, William Donaldson
Reactivity Of Acyclic (Pentadienyl)Iron(1+) Cations: Synthetic Studies Directed Toward The Frondosins, Do W. Lee, Rajesh K. Pandey, Sergey Lindeman, William Donaldson
Chemistry Faculty Research and Publications
A short, 4-step route to the scaffold of frondosin A and B is reported. The [1-methoxycarbonyl-5-(2′,5′-dimethoxyphenyl)pentadienyl]Fe(CO)3+ cation was prepared in two steps from (methyl 6-oxo-2,4-hexadienoate)Fe(CO)3. Reaction of this cation with isopropenyl Grignard or cyclohexenyllithium reagents affords (2-alkenyl-5-aryl-1-methoxycarbonyl-3-pentene-1,5-diyl)Fe(CO)3 along with other addition products. Oxidative decomplexation of these (pentenediyl)iron complexes, utilizing CuCl2, affords 6-aryl-3-methoxycarbonyl-1,4-cycloheptadienes via the presumed intermediacy of a cis-divinylcyclopropane.
Reactivity Of (2-Alkenyl-3-Pentene-1,5-Diyl)Iron Complexes: Preparation Of Functionalized Vinylcyclopropanes And Cycloheptadienes, Rajesh K. Pandey, Lizhu Wang, Nathaniel J Wallock, Sergey Lindeman, William Donaldson
Reactivity Of (2-Alkenyl-3-Pentene-1,5-Diyl)Iron Complexes: Preparation Of Functionalized Vinylcyclopropanes And Cycloheptadienes, Rajesh K. Pandey, Lizhu Wang, Nathaniel J Wallock, Sergey Lindeman, William Donaldson
Chemistry Faculty Research and Publications
The reactivity of (2-alkenyl-3-pentene-1,5-diyl)iron complexes toward olefin metathesis, cycloaddition, and mild oxidations (MnO2 or mCPBA) was examined. Cycloaddition reactions were observed to occur with modest diastereoselectivity (33−63% de). Decomplexation of the (3-pentenediyl) ligand may be accomplished by oxidation with either CAN or alkaline hydrogen peroxide to afford vinylcyclopropanecarboxylates or divinylcyclopropanecarboxylates. Reduction of the latter, followed by Cope rearrangement generates cycloheptadienylmethanols. These studies demonstrate that (2-alkenyl-3-pentene-1,5-diyl)iron complexes can serve as organometallic scaffolds for the preparation of a wide variety of structural motifs containing up to 5 contiguous stereocenters.
The Electrochemical Oxidation Of Organic Selenides And Selenoxides, Michael D. Ryan, Jiyi Yau, Michael Hack
The Electrochemical Oxidation Of Organic Selenides And Selenoxides, Michael D. Ryan, Jiyi Yau, Michael Hack
Chemistry Faculty Research and Publications
The electrochemical oxidation of alkyl and aryl selenides was investigated in acetonitrile. The oxidation of diphenyl selenide and di(4‐methylphenyl) selenide led primarily to the formation of their respective selenoxides, which were identified by exhaustive coulometric oxidation and and analysis of the products. The selenoxide itself was not observed in the cyclic voltammetry of the selenide for two reasons: first, the protonation of the selenoxide by the acid formed from the reaction of water with the cation radical and second, the formation of a selenoxide hydrate. The formation of the hydrate with diphenyl selenoxide was verified by isolation of the dimethoxy …
The Electrochemical Oxidation Of Substituted Catechols, Michael D. Ryan, Alice Yueh, Wen-Yu Chen
The Electrochemical Oxidation Of Substituted Catechols, Michael D. Ryan, Alice Yueh, Wen-Yu Chen
Chemistry Faculty Research and Publications
The oxidation of substituted catechols was studied by cyclic voltammetry, chronoamperometry, rotating ring‐disk electrode, and coulometry. The results showed that the quinones that were formed from the oxidation of substituted catechols reacted with the basic forms of the starting material to yield the dimeric product. These products were generally unstable and rapidly polymerized or underwent some other irreversible reaction to form an electroinactive product. For 3,4‐dihydroxyacetophenone and propriophenone, the intermediate was stable long enough to be observed in cyclic voltammetry. The rate of the coupling reaction was found to correlate well with the Hammett ρ‐σ parameters and indicated that there …