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dc.contributor.authorRobinson, Julia M.
dc.contributor.authorSakai, Takeo
dc.contributor.authorOkano, Katsuhiko
dc.contributor.authorKitawaki, Takafumi
dc.contributor.authorDanheiser, Rick Lane
dc.date.accessioned2011-12-16T17:00:07Z
dc.date.available2011-12-16T17:00:07Z
dc.date.issued2010-07
dc.identifier.issn0002-7863
dc.identifier.issn1520-5126
dc.identifier.urihttp://hdl.handle.net/1721.1/67701
dc.descriptionExperimental procedures, characterization data, and [superscript 1]H and [superscript 13]C NMR spectra for all new compounds. This material is available free of charge via the Internet at http://pubs.acs.org.en_US
dc.description.abstractA formal, metal-free, [2 + 2 + 2] cycloaddition strategy is described based on a cascade of two pericyclic processes. The first step involves an intramolecular propargylic ene reaction of a 1,6-diyne to generate a vinylallene, which then reacts in an inter- or intramolecular Diels−Alder reaction with an alkenyl or alkynyl dienophile. Reactions involving unsymmetrical alkenyl and alkynyl dienophiles proceed with good to excellent regioselectivity, and the diastereoselectivity in the Diels−Alder step is also high, with endo cycloadducts produced as the exclusive products of the reaction. In the case of alkynyl dienophiles, [4 + 2] cycloaddition initially generates an isotoluene-type intermediate that isomerizes to the isolated aromatic product upon exposure to a catalytic amount of DBU at room temperature. The mechanism of several earlier fully intramolecular related transformations have been shown to involve an analogous process rather than the diradical-mediated pathways proposed previously.en_US
dc.description.sponsorshipBoehringer Ingelheim Pharmaceuticalsen_US
dc.description.sponsorshipNational Science Foundation (U.S.)en_US
dc.description.sponsorshipAstraZeneca (Firm)en_US
dc.description.sponsorshipJapan Society for the Promotion of Scienceen_US
dc.description.sponsorshipNational Institutes of Health (U.S.) (GM 28273)en_US
dc.description.sponsorshipMerck Research Laboratoriesen_US
dc.description.sponsorshipDaiichi Sankyo Co.en_US
dc.language.isoen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.isversionofhttp://dx.doi.org/10.1021/ja1053829en_US
dc.rightsArticle is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.en_US
dc.sourceProf. Danheiser via Erja Kajosaloen_US
dc.titleFormal [2+2+2] Cycloaddition Strategy Based on an Intramolecular Propargylic Ene Reaction/Diels-Alder Cycloaddition Cascadeen_US
dc.typeArticleen_US
dc.identifier.citationRobinson, Julia M. et al. “Formal [2 + 2 + 2] Cycloaddition Strategy Based on an Intramolecular Propargylic Ene Reaction/Diels−Alder Cycloaddition Cascade.” Journal of the American Chemical Society 132 (2010): 11039-11041. Web. 16 Dec. 2011. © 2011 American Chemical Societyen_US
dc.contributor.departmentMassachusetts Institute of Technology. Department of Chemistryen_US
dc.contributor.approverDanheiser, Rick
dc.contributor.mitauthorRobinson, Julia M.
dc.contributor.mitauthorSakai, Takeo
dc.contributor.mitauthorOkano, Katsuhiko
dc.contributor.mitauthorKitawaki, Takafumi
dc.contributor.mitauthorDanheiser, Rick Lane
dc.relation.journalJournal of the American Chemical Societyen_US
dc.eprint.versionAuthor's final manuscripten_US
dc.type.urihttp://purl.org/eprint/type/JournalArticleen_US
eprint.statushttp://purl.org/eprint/status/PeerRevieweden_US
dspace.orderedauthorsRobinson, Julia M.; Sakai, Takeo; Okano, Katsuhiko; Kitawaki, Takafumi; Danheiser, Rick L.en
dc.identifier.orcidhttps://orcid.org/0000-0002-9812-206X
mit.licensePUBLISHER_POLICYen_US
mit.metadata.statusComplete


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