dc.contributor.author | Robinson, Julia M. | |
dc.contributor.author | Sakai, Takeo | |
dc.contributor.author | Okano, Katsuhiko | |
dc.contributor.author | Kitawaki, Takafumi | |
dc.contributor.author | Danheiser, Rick Lane | |
dc.date.accessioned | 2011-12-16T17:00:07Z | |
dc.date.available | 2011-12-16T17:00:07Z | |
dc.date.issued | 2010-07 | |
dc.identifier.issn | 0002-7863 | |
dc.identifier.issn | 1520-5126 | |
dc.identifier.uri | http://hdl.handle.net/1721.1/67701 | |
dc.description | Experimental 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.abstract | A 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.sponsorship | Boehringer Ingelheim Pharmaceuticals | en_US |
dc.description.sponsorship | National Science Foundation (U.S.) | en_US |
dc.description.sponsorship | AstraZeneca (Firm) | en_US |
dc.description.sponsorship | Japan Society for the Promotion of Science | en_US |
dc.description.sponsorship | National Institutes of Health (U.S.) (GM 28273) | en_US |
dc.description.sponsorship | Merck Research Laboratories | en_US |
dc.description.sponsorship | Daiichi Sankyo Co. | en_US |
dc.language.iso | en_US | |
dc.publisher | American Chemical Society | en_US |
dc.relation.isversionof | http://dx.doi.org/10.1021/ja1053829 | en_US |
dc.rights | Article 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.source | Prof. Danheiser via Erja Kajosalo | en_US |
dc.title | Formal [2+2+2] Cycloaddition Strategy Based on an Intramolecular Propargylic Ene Reaction/Diels-Alder Cycloaddition Cascade | en_US |
dc.type | Article | en_US |
dc.identifier.citation | Robinson, 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 Society | en_US |
dc.contributor.department | Massachusetts Institute of Technology. Department of Chemistry | en_US |
dc.contributor.approver | Danheiser, Rick | |
dc.contributor.mitauthor | Robinson, Julia M. | |
dc.contributor.mitauthor | Sakai, Takeo | |
dc.contributor.mitauthor | Okano, Katsuhiko | |
dc.contributor.mitauthor | Kitawaki, Takafumi | |
dc.contributor.mitauthor | Danheiser, Rick Lane | |
dc.relation.journal | Journal of the American Chemical Society | en_US |
dc.eprint.version | Author's final manuscript | en_US |
dc.type.uri | http://purl.org/eprint/type/JournalArticle | en_US |
eprint.status | http://purl.org/eprint/status/PeerReviewed | en_US |
dspace.orderedauthors | Robinson, Julia M.; Sakai, Takeo; Okano, Katsuhiko; Kitawaki, Takafumi; Danheiser, Rick L. | en |
dc.identifier.orcid | https://orcid.org/0000-0002-9812-206X | |
mit.license | PUBLISHER_POLICY | en_US |
mit.metadata.status | Complete | |