Stereoelectronic Control in Diels−Alder Reaction of Dissymmetric 1,3-Dienes
- 11 February 2000
- journal article
- Published by American Chemical Society (ACS) in Accounts of Chemical Research
- Vol. 33 (5) , 278-286
- https://doi.org/10.1021/ar990123s
Abstract
The Diels-Alder reaction is a widely employed protocol in which four stereogenic centers are generated in a predictable manner with olefin geometry, adjoining chiral center, and transition-state topology serving as the main controlling elements. However, when the Diels-Alder partners are in a dissymmetric environment, pi-face selection is determined through the interplay of steric, orbital, and electrostatic factors whose relative importance is a subject of intense debate. Several new systems have been crafted to probe the mechanistic nuances of the pi-face selection. The available data have enabled us to qualitatively define a hierarchy of various stereoelectronic effects that would aid predictability of the stereochemical outcome.Keywords
This publication has 27 references indexed in Scilit:
- Harvesting Diels and Alder's Garden: Synthetic Investigations of Intramolecular [4 + 2] CycloadditionsAccounts of Chemical Research, 1999
- Intramolecular Diels–Alder ReactionsPublished by Elsevier ,1991
- Functionalized 1,2-dioxetanes as potential phototherapeutic agents: the synthesis of carboxylate, carbonate, carbamate, and ether derivatives of 3-(hydroxymethyl)-3,4,4-trimethyl-1,2-dioxetaneThe Journal of Organic Chemistry, 1987
- Stereochemical aspects of the intramolecular Diels–Alder reactionChemical Society Reviews, 1987
- Diels-Alder reactions of cycloalkenones. 10. Endo-exo diastereoselectivity of 2-cyclohexenonesThe Journal of Organic Chemistry, 1986
- The intramolecular Diels–Alder reaction: recent advances and synthetic applicationsCanadian Journal of Chemistry, 1984
- .sigma./.pi. Interaction as a controlling factor in the stereoselectivity of addition reactionsAccounts of Chemical Research, 1983
- The π‐Anisotropy of the Double Bond of a syn‐11‐Oxasesquinorbornene Derivative.. Stereoselectivity of the Diels–Alder additions of (2‐norborneno)[c]furan. Crystal structure of 11‐oxa‐endo‐tetracyclo[6.2.1.13,6.02,7]‐dodec‐2(7)‐ene‐9,10‐exo‐dicarboxylic anhydrideHelvetica Chimica Acta, 1981
- Propellanes. XLVI. Steric and electronic effects as observed in reactions of propellanesPublished by Walter de Gruyter GmbH ,1979
- Molecular orbital studies of the protonation of the methylanisolesJournal of the American Chemical Society, 1976