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kornblum delamare rearrangement wikipedia jump to content main menu main menu move to sidebar hide navigation main page contents current events random article about wikipedia contact us contribute help learn to edit community portal recent changes upload file special pages search search appearance donate create account log in personal tools donate create account log in contents move to sidebar hide top 1 reaction mechanism 2 related reactions 3 scope 4 references toggle the table of contents kornblum delamare rearrangement 3 languages deutsch فارسی 中文 edit links article talk english read edit view history tools tools move to sidebar hide actions read edit view history general what links here related changes upload file permanent link page information cite this page get shortened url switch to legacy parser print export download as pdf printable version in other projects wikimedia commons wikidata item appearance move to sidebar hide from wikipedia the free encyclopedia rearrangement reaction in organic chemistry the kornblum delamare rearrangement is a rearrangement reaction in organic chemistry in which a primary or secondary organic peroxide is converted to the corresponding ketone and alcohol under acid or base catalysis the reaction is relevant as a tool in organic synthesis and is a key step in the biosynthesis of prostaglandins 1 the base can be a hydroxide such as potassium hydroxide or an amine such as triethylamine reaction mechanism edit in the reaction mechanism for this organic reaction the base abstracts the acidic α proton of the peroxide 1 to form the carbanion 4 as a reactive intermediate which rearranges to the ketone 2 with expulsion of the hydroxyl anion 3 this intermediate gains a proton forming the alcohol 3 deprotonation and rearrangement can also be a concerted reaction without formation of 4 an alternative reaction mechanism involving direct nucleophilic displacement on the peroxide link of the amine followed by an elimination reaction is considered unlikely based on the outcome of this model reaction 2 the peroxide 1 converts to the hydroxyketone 2 by action of triethylamine but the alternative route through hydroxylamine 3 by nucleophilic displacement with lithium diisopropylamide and the ammonium salt 4 by methylation with methyl trifluoromethanesulfonate fails the reaction formally a rearrangement ranks under the elimination reactions as already observed by the original authors not only alkoxides but any leaving group capable of carrying a negative charge will do for instance nitrate esters r c r h o no 2 related reactions edit the corresponding reaction involving an ether is the 1 2 wittig rearrangement the reaction course in this rearrangement is different because ether cleavage with carbanion formation is unfavorable the pummerer rearrangement in one of its reaction step contains a sulfur variation scope edit the original 1951 publication concerned the conversion of potassium t butyl peroxide and 1 phenylethyl bromide to ultimately acetophenone and t butanol with piperidine as the base the kornblum delamare rearrangement can be carried out as an asymmetric reaction with a suitable chiral amine such as sparteine or a cinchona alkaloid 3 the first step in this one pot reaction is 1 4 dioxygenation of 1 3 cycloheptadiene with singlet oxygen and a tpp catalyst references edit the base catalyzed decomposition of a dialkyl peroxide nathan kornblum and harold e delamare j am chem soc 1951 73 2 pp 880 81 doi 10 1021 ja01146a542 the mechanism of the tertiary amine catalysed isomerisation of endoperoxides to hydroxyketones synthesis and chemistry of the intermediate postulated in the peroxide attack mechanism david r kelly harjinder bansal and j j gwynfor morgan tetrahedron letters volume 43 issue 51 16 december 2002 pages 9331 9333 doi 10 1016 s0040 4039 02 02374 2 enantioselective synthesis of hydroxyenones by chiral base catalyzed kornblum delamare rearrangement steven t staben xin linghu and f dean toste j am chem soc 2006 128 39 pp 12658 12659 communication doi 10 1021 ja065464x retrieved from https en wikipedia org w index php title kornblum delamare_rearrangement oldid 1372417460 categories organic redox reactions rearrangement reactions name reactions hidden categories articles with short description short description matches wikidata use dmy dates from april 2023 this page was last edited on 31 august 2026 at 17 19 utc page was rendered with parsoid text is available under the creative commons attribution sharealike 4 0 license additional terms may apply by using this site you agree to the terms of use and privacy policy wikipedia is a registered trademark of the wikimedia foundation inc a non profit organization privacy policy about wikipedia disclaimers contact wikipedia legal safety contacts code of conduct developers statistics cookie statement mobile view search search toggle the table of contents kornblum delamare rearrangement 3 languages add topic