Oxygen cyclic ketones

According to Quinkert, photoexcited cyclic ketones may be transformed to open-chain unsaturated carboxylic acids in the presence of molecular oxygen. This reaction may compete efficiently with a-cleavage and secondary transformations thereof. Thus, both stereo iso meric 17-ketones (109) and (110) yield as much as 20% of the unsaturated acid (111) when irradiated in benzene under a stream of oxygen. This photolytic autoxidation has been used notably for partial syntheses of naturally occurring unsaturated 3,4-seco-acids from 3-oxo triterpenes (for references, see ref. 72). 

The ring-opening of the cyclopropane nitrosourea 233 with silver trifiate followed by stereospecific [4 + 2] cycloaddition yields 234 [129]. (Scheme 93) Oxovanadium(V) compounds, VO(OR)X2, are revealed to be Lewis acids with one-electron oxidation capability. These properties permit versatile oxidative transformations of carbonyl and organosilicon compounds as exemplified by ring-opening oxygenation of cyclic ketones [130], dehydrogenative aroma-tization of 2-eyclohexen-l-ones [131], allylic oxidation of oc,/ -unsaturated carbonyl compounds [132], decarboxylative oxidation of a-amino acids [133], oxidative desilylation of silyl enol ethers [134], allylic silanes, and benzylic silanes [135]. 

The reaction of 2-chloro-4,5-dihydroimidazole 347 with hydroxylamine-O-sulfonic acid gives 2-hydroxylamino-4,5-dihydroimidazolium-O-sulfonate 348, which reacts with aldehydes and cyclic ketones to give the imidazo[l,2-f] fused 4,5-dihydro-l,2,4-oxadiazoles 350 (Scheme 58). Mechanistically, the reaction may be explained by the reaction of an imidazoline NH with the carbonyl followed by intramolecular electrophilic amination of the anionic oxygen present in the resultant intermediate 349 and elimination of the sulfate group <2003JOC4791>. 

Singh and coworkers have carried ont a large amonnt of work on the synthesis of sprro 1,2,4-trioxanes by employing the ene reaction of singlet oxygen with substituted ally lie alcohols The resulting hydroperoxy alcohols 86a can be condensed with a variety of different carbonyl compounds inclnding cyclic ketones (Scheme 33). Some of these trioxanes 86b have excellent in vivo activity (see Table 1). 

Most photodecarbonylation reactions of cyclic ketones, especially in the vapor phase, have been postulated to proceed from various vibrational levels of excited singlet states.321 However, the elimination reaction leading to unsaturated aldehydes has now been shown to occur largely via excited triplet states. In solution, where the lowest vibrational levels of the excited states are rapidly reached, to-alkenals are the major products observed in both photolysis and radiolysis of cyclopentanone and cyclohexanone. The reaction is quenched by oxygen and dienes,322-324 as well as by the alkenal produced in the reaction.325 The reaction is also sensitized by benzene triplets.322,323 With cyclopentanone, quenching by 1M piperylene occurs some 20 times as fast... 

The photolysis of cyclic ketones, in general, results in homolytic cleavage of the carbon-carbon bond adjacent to the carbonyl function. For details of this process, the reader is referred to the review by Srinivasan.425 Included among the photoproducts are certain oxygen heterocycles, formed by cyclization of reactive intermediates. Thus, cleavage in a cyclic /3-diketone, such as tetramethylcyclobutane-1,3-dione or hexamethylcyclohexane-l,3,5-trione [Eq. (110)] is followed by cyclization on the oxygen atom to form a lactone.426,427 y-Lactone formation is also observed on photolysis of 2,2-diphenylindane-l,3-dione [Eq. (Ill)] in ether, and the process is reversible.428... 

Harrison and Jennings463 studied the reactions of the negative oxygen ion O " with methyl-, dialkyl- and some cyclic ketones. The main reactions are ... 

The CCl4-HF-SbF5 system developed by Jouannetaud and co-workers and used in the selective fluorination of imines (see Section 5.10.1) can be applied in the oxygenation of ketones and carboxamides as well. The hydroxylation of ketones is selective [Eq. (5.229)], provided that a five- or six-membered cyclic carboxonium ion preventing fluorination is involved.534,659 Fluorination, however, may be a side reaction with product distributions depending on quenching conditions (aqueous Na2CC>3 or HF-pyridine). Similar features are characteristic of the transformation of carboxamides.659... 

HLADH was applied for the reduction of a broad variety of substrates. The regeneration of NADH can be achieved by the ethanol coupled-substrate method [239]. Cyclic ketones are good substrates for this enzyme [137, 240, 241]. Heterocyclic compounds containing oxygen or sulfur are accepted, too [242 246], but nitrogen-containing substrates are inhibitors of HLADH, because they apparently complex with zinc in the active site of the enzyme [247],... 

Highly selective to halogenated and oxygenated compounds Electron capture detector EDB, DBCP (EPA 8011) Acrylamide (EPA 8032) Phenols (EPA 8041) Phthalates (EPA 8061) Organochlorine pesticides (EPA 8081) PCBs (EPA 8082) Nitroaromatics and cyclic ketones (EPA 8091) Haloethers (EPA 8111) Chlorinated herbicides (EPA 8151) CLP SOW for organic analysis Interferences from Elemental sulfur (S8) Waxes, lipids, other high molecular weight compounds Phthalate esters, which are common laboratory contaminants Oil in PCB analysis... 

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