Diastereoselectivities in the diels-alder reactions of cyclopentadiene with optically active dimenthyl fumarate and menthyl methyl fumarate in LiClO4/ether and on Al2O3

Satinder Bains, Richard M. Pagni, George Kabalka, Catherine Pala

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

Reactions of cyclopentadiene with (-)-dimenthyl fumarate, which yield adducts 1 and 2, and with (-)-menthyl methyl fumarate, which yield adducts 3 through 6, were carried out on alumina activated at different temperatures, in LiClO4/ether solutions, and in other media. Various diastereoselectivities - 2:1,3:4, 6:5, endo:exo [(3+4): (5+6)], and % de [(3+6) - (4+5)]/[3+4+5+6] × 100] - were determined for these reactions. The LiClO4 data were analyzed using a model in which LiClO4 reversibly binds to the dienophile, resulting in competing catalyzed and uncatalyzed Diels-Alder reactions. Even in approximately 5 M LiClO4, there are sizable contributions from uncatalyzed reactions in all cases. Extrapolation of the data to infinite LiClO4 concentration yields data for the catalyzed reactions alone; only modest diastereoselectivities are seen for the catalyzed reactions. The alumina results were unusual because the endo:exo ratios of adducts were large but % de's were small. The selectivities on alumina could not be correlated to the activity of the solid. This behavior will occur when varying numbers and types of catalytic sites are exposed to the surface on activation.

Original languageEnglish (US)
Pages (from-to)821-834
Number of pages14
JournalTetrahedron: Asymmetry
Volume5
Issue number5
DOIs
StatePublished - Jan 1 1994
Externally publishedYes

Fingerprint

Cyclopentanes
Diels-Alder reactions
Fumarates
Ether
Ethers
ethers
Alumina
Activated alumina
adducts
Extrapolation
aluminum oxides
Aluminum Oxide
Chemical activation
extrapolation
Temperature
selectivity
lithium perchlorate
activation

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Diastereoselectivities in the diels-alder reactions of cyclopentadiene with optically active dimenthyl fumarate and menthyl methyl fumarate in LiClO4/ether and on Al2O3. / Bains, Satinder; Pagni, Richard M.; Kabalka, George; Pala, Catherine.

In: Tetrahedron: Asymmetry, Vol. 5, No. 5, 01.01.1994, p. 821-834.

Research output: Contribution to journalArticle

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abstract = "Reactions of cyclopentadiene with (-)-dimenthyl fumarate, which yield adducts 1 and 2, and with (-)-menthyl methyl fumarate, which yield adducts 3 through 6, were carried out on alumina activated at different temperatures, in LiClO4/ether solutions, and in other media. Various diastereoselectivities - 2:1,3:4, 6:5, endo:exo [(3+4): (5+6)], and {\%} de [(3+6) - (4+5)]/[3+4+5+6] × 100] - were determined for these reactions. The LiClO4 data were analyzed using a model in which LiClO4 reversibly binds to the dienophile, resulting in competing catalyzed and uncatalyzed Diels-Alder reactions. Even in approximately 5 M LiClO4, there are sizable contributions from uncatalyzed reactions in all cases. Extrapolation of the data to infinite LiClO4 concentration yields data for the catalyzed reactions alone; only modest diastereoselectivities are seen for the catalyzed reactions. The alumina results were unusual because the endo:exo ratios of adducts were large but {\%} de's were small. The selectivities on alumina could not be correlated to the activity of the solid. This behavior will occur when varying numbers and types of catalytic sites are exposed to the surface on activation.",
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