Highly selective Diels-Alder reactions of directly connected enyne dienophiles Journal Article


Authors: Dai, M.; Sarlah, D.; Yu, M.; Danishefsky, S. J.; Jones, G. O.; Houk, K. N.
Article Title: Highly selective Diels-Alder reactions of directly connected enyne dienophiles
Abstract: The paper describes the course of cycloadditions of Diels-Alder dienophiles containing linked enyne sites, each substituted with activating groups. Consistently, it was found that in the enyne cases the Diels-Alder reaction occurred specifically at the acetylenic center. Furthermore, it was found that the regiochemical sense of the cycloaddition was apparently determined by the remote activating group bound to the olefinic site. This remote acrylyl group totally dominated the course of the cycloaddition, relative to the activating group bound directly on the acetylene site. Explanations for these findings at the computational level are provided. The computations also rationalize the strong preference for cycloaddition to occur at the acetylene linkage and encompass the otherwise surprising regiochemical dominance by the remote ester on the olefinic site. The high selectivities available through such reactions provide important new opportunities in the synthesis of orsenillate type substructures that are found in a variety of natural products of contemporary interest. © 2007 American Chemical Society.
Keywords: chemical analysis; algorithms; magnetic resonance spectroscopy; chemical structure; molecular structure; catalysis; cyclization; dienophiles; diels alder reaction; models, chemical; chemical reaction; stereochemistry; esters; chemical bond; cycloaddition; acetylene; alkadienes; aromatization; reaction kinetics; addition reactions; diels alder reactions; enynes; unsaturated compounds; acetylene derivative
Journal Title: Journal of the American Chemical Society
Volume: 129
Issue: 3
ISSN: 0002-7863
Publisher: American Chemical Society  
Date Published: 2007-01-24
Start Page: 645
End Page: 657
Language: English
DOI: 10.1021/ja065762u
PUBMED: 17227028
PROVIDER: scopus
DOI/URL:
Notes: --- - "Cited By (since 1996): 20" - "Export Date: 17 November 2011" - "CODEN: JACSA" - "Source: Scopus"
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