- Reactions of Bis(N,N'-bicyclic) Diazenium Dications
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Eleven bis(N,N'-bicyclic) diazenium dications were generated from the corresponding hydrazines by NOPF6 oxidation.Their reactivity depends greatly upon the sizes of the bicyclic rings. (We designate bicyclic ring size using the number of atoms in the two bridges in addition to the dinitrogen bridge all the compound share.) Compounds with rings alkylate acetonitrile at 240 K by opening a Cα-N(+) bond to produce a trialkyldiazenium cation, with ΔG(excit.) for the reaction increasing by at least 5.5 kcal/mol as the second bicyclic ring size increases.Compounds with an unsaturated bridge also alkylate acetonitrile; 22/u22(2+) only cleaves the bridge and reacts faster than 21/22(2+), which only cleaves the bridge.Cα-N(+) cleavage of and larger rings by acetonitrile has not been observed. 21/22(2+) is significantly more acidic than 22/22(2+), but both are β-deprotonated by pyridine to produce aminoaziridinium cations at 240 K.At least mostly the exo ring proton is lost from 21/22(2+).Dications with and bridges deprotonate at the α-carbon instead of the β-carbon, and 22/23(2+) is slightly more kinetically acidic than 21/22(2+). 22/24(2+) is deprotonated rapidly by ether at 235 K.
- Nelsen, Stephen F.,Wang, Yichun
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- Reductive Electrochemical Activation of Molecular Oxygen Catalyzed by an Iron-Tungstate Oxide Capsule: Reactivity Studies Consistent with Compound i Type Oxidants
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The reductive activation of molecular oxygen catalyzed by iron-based enzymes toward its use as an oxygen donor is paradigmatic for oxygen transfer reactions in nature. Mechanistic studies on these enzymes and related biomimetic coordination compounds designed to form reactive intermediates, almost invariably using various "shunt" pathways, have shown that high-valent Fe(V)=O and the formally isoelectronic Fe(IV) =O porphyrin cation radical intermediates are often thought to be the active species in alkane and arene hydroxylation and alkene epoxidation reactions. Although this four decade long research effort has yielded a massive amount of spectroscopic data, reactivity studies, and a detailed, but still incomplete, mechanistic understanding, the actual reductive activation of molecular oxygen coupled with efficient catalytic transformations has rarely been experimentally studied. Recently, we found that a completely inorganic iron-tungsten oxide capsule with a keplerate structure, noted as {Fe30W72}, is an effective electrocatalyst for the cathodic activation of molecular oxygen in water leading to the oxidation of light alkanes and alkenes. The present report deals with extensive reactivity studies of these {Fe30W72} electrocatalytic reactions showing (1) arene hydroxylation including kinetic isotope effects and migration of the ipso substituent to the adjacent carbon atom ("NIH shift"); (2) a high kinetic isotope effect for alkyl C - H bond activation; (3) dealkylation of alkylamines and alkylsulfides; (4) desaturation reactions; (5) retention of stereochemistry in cis-alkene epoxidation; and (6) unusual regioselectivity in the oxidation of cyclic and acyclic ketones, alcohols, and carboxylic acids where reactivity is not correlated to the bond disassociation energy; the regioselectivity obtained is attributable to polar effects and/or entropic contributions. Collectively these results also support the conclusion that the active intermediate species formed in the catalytic cycle is consistent with a compound I type oxidant. The activity of {Fe30W72} in cathodic aerobic oxidation reactions shows it to be an inorganic functional analogue of iron-based monooxygenases.
- Bugnola, Marco,Shen, Kaiji,Haviv, Eynat,Neumann, Ronny
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p. 4227 - 4237
(2020/05/05)
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- Combined effects on selectivity in Fe-catalyzed methylene oxidation
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Methylene C-H bonds are among the most difficult chemical bonds to selectively functionalize because of their abundance in organic structures and inertness to most chemical reagents. Their selective oxidations in biosynthetic pathways underscore the power of such reactions for streamlining the synthesis of molecules with complex oxygenation patterns. We report that an iron catalyst can achieve methylene C-H bond oxidations in diverse natural-product settings with predictable and high chemo-, site-, and even diastereoselectivities. Electronic, steric, and stereoelectronic factors, which individually promote selectivity with this catalyst, are demonstrated to be powerful control elements when operating in combination in complex molecules. This small-molecule catalyst displays site selectivities complementary to those attained through enzymatic catalysis.
- Chen, Mark S.,White, M. Christina
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scheme or table
p. 533 - 571
(2010/10/05)
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- CoTPP-CATALYZED REACTION OF SATURATED BICYCLIC ENDOPEROXIDES
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Saturated bicyclic endoperoxides were exposed to CoTPP (Cobalt-mesotetraphenylporphyrine) in chloroform, the peroxyde bond was cleaved and a mixture of products arising from fragmentation and reduction obtained.
- Balci, Metin,Akbulut, Nihat
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p. 1315 - 1322
(2007/10/02)
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- Formation of Dicarbonyl Compounds in the Flash Vacuum Pyrolysis of Saturated Bicyclic Peroxides
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Under flash vacuum pyrolysis, dioxabicycloalkanes (n = 3,4, and 5) isomerise to keto-aldehydes, MeCOnCHO, whereas dioxabicycloalkanes (n = 2,3, and 4) fragment to give, by loss of hydrogen and ethylene, mixtures of cycloalkane-1,4-diones and dialdehydes, OHCnCHO.
- Bloodworth, A. J.,Baker, David S.,Eggelte, Henny J.
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p. 1034 - 1036
(2007/10/02)
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