Synthesis Of Indolizidines And Pyrrolizidines Through The [2 + 2]cycloaddition Of Five-membered Endocyclic Enecarbamates To Alkyl Ketenes. Unusual Regioselectivity Of Baeyer-villiger Ring Expansions Of Alkyl Aza-bicyclic Cyclobutanones.

dc.creatorde Faria, Antonio R
dc.creatorSalvador, Elias L
dc.creatorCorreia, Carlos Roque D
dc.date2002-May
dc.date2015-11-27T12:49:38Z
dc.date2015-11-27T12:49:38Z
dc.date.accessioned2018-03-29T00:57:15Z
dc.date.available2018-03-29T00:57:15Z
dc.identifierThe Journal Of Organic Chemistry. v. 67, n. 11, p. 3651-61, 2002-May.
dc.identifier0022-3263
dc.identifier
dc.identifierhttp://www.ncbi.nlm.nih.gov/pubmed/12027676
dc.identifierhttp://repositorio.unicamp.br/jspui/handle/REPOSIP/195336
dc.identifier12027676
dc.identifier.urihttp://repositorioslatinoamericanos.uchile.cl/handle/2250/1295569
dc.descriptionThe total syntheses of two indolizidine skeletons and of the necine base (+/-)-platynecine were accomplished in a concise manner with good overall yields starting from a common five-membered endocyclic enecarbamate. These syntheses feature a [2 + 2]cycloaddition of the five-membered endocyclic enecarbamate 5 to alkylketenes that proceeded in high yields and with high stereoselectivity to provide an endo alkyl cycloadduct as the major or only product. The minor exo alkyl cycloadducts, which can be observed in some [2 + 2]cycloadditions, seem to derive from the endo cycloadduct, the putative kinetic product, by epimerization. An unusual regioselectivity was observed for the Baeyer-Villiger oxidation of 7-alkyl-2-azabicyclic cyclobutanones. Endo-7-alkyl cycloadducts ring-expanded exclusively to a gamma-lactone in which oxygen is inserted into the C6-C7 bond in preference to the bridgehead C5-C6 bond. With the exo-7-alkyl cycloadduct the regioselectivity of the Baeyer-Villiger oxidation is drastically reduced, leading to mixtures of regioisomeric lactones in a ratio of approximately 1.5 to 1. It is hypothesized that the steric strain built into the Criegee cyclobutane intermediate is the regioselective controlling factor in these oxidations, overriding any stereoelectronic bias for ring expansion. A rationale for the mechanism of the [2 + 2]cycloaddition involving enecarbamates and ketenes is presented, which seems to involve the participation of an N-acyliminium-enolate intermediate.
dc.description67
dc.description3651-61
dc.languageeng
dc.relationThe Journal Of Organic Chemistry
dc.relationJ. Org. Chem.
dc.rightsfechado
dc.rights
dc.sourcePubMed
dc.subjectCarbamates
dc.subjectCyclobutanes
dc.subjectEthylenes
dc.subjectIndole Alkaloids
dc.subjectIndolizines
dc.subjectKetones
dc.subjectPyrrolizidine Alkaloids
dc.titleSynthesis Of Indolizidines And Pyrrolizidines Through The [2 + 2]cycloaddition Of Five-membered Endocyclic Enecarbamates To Alkyl Ketenes. Unusual Regioselectivity Of Baeyer-villiger Ring Expansions Of Alkyl Aza-bicyclic Cyclobutanones.
dc.typeArtículos de revistas


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