Regioselectivity control in Diels-Alder reactions of surfactant 1,3- dienes with surfactant dienophiles

David A. Jaeger, Dan Su, Abdullah Zafar, Barbora Piknova, Stephen B. Hall

Research output: Contribution to journalArticle

26 Scopus citations

Abstract

The ability of surfactant aggregate-H2O interfaces to control the regioselectivity of Diels-Alder reactions has been investigated. Cycloadditions of surfactant 1,3-dienes 2-[[3-(dimethyldodecylsilyl)-1,3- butadien-2-yl]thio]-N,N,N-trimethyl-1-ethanaminium iodide (1a) and 6-[[3- (dimethyloctylsilyl)-1,3-butadien-2-yl]thio]-N,N,N-trimethyl-1-hexanaminium iodide (1b) with surfactant dienophiles (E)-2-[[[2- (dodecoxycarbonyl)ethenyl]carbonyl]oxy]-N,N,N-trimethyl-1-ethanaminium iodide (2a) and (E)-6-[[[2-(octoxycarbonyl)ethenyl]carbonyl]oxy]-N,N,N-trimethyl-1- hexanaminium bromide (2b) within their aqueous mixed micelles have been performed at 25(35) °C. The cycloaddition of 1a and 2a gave a 30:1 ratio of trans-1-[(2-trimethylammonio)ethylthio]-2-(dimethyldodecylsilyl)-4- (dodecoxycarbonyl)-5-[(2-trimethylammonio)ethoxycarbonyl]-1-cyclohexene dihalide (15a) and trans-1-[(2-trimethylammonio)ethylthio]-2- (dimethyldodecylsilyl)-4-[(2-trimethylammonio)ethoxycarbonyl]-5- (dodecoxycarbonyl)-1-cyclohexene dihalide (16a), respectively, and that of 1b and 2b a 6.6:1 ratio of trans-1-[(6-trimethylammonio)hexylthio]-2- (dimethyloctylsilyl)-4-(octoxycarbonyl)-5-[6- (trimethylammonio)hexoxycarbonyl]-1-cyclohexene dihalide (15b) and trans-1- [(6-trimethylammonio)hexylthio]-2-(dimethyloctylsilyl)-4-[6- (trimethylammonio)hexoxycarbonyl]-5-(octoxycarbonyl)-1-cyclohexene dihalide (16b), respectively. The excess of 15 over 16 is consistent with the reaction of 1 and 2 within mixed aggregates in their preferred orientations at the aggregate-H2O interface. The greater regioselectivity obtained in the reaction of 1a and 2a is ascribed to the shorter tether between their reactive functional groups and quaternary ammonium headgroups. A monolayer study of 15a and 16a was also performed.

Original languageEnglish (US)
Pages (from-to)2749-2757
Number of pages9
JournalJournal of the American Chemical Society
Volume122
Issue number12
DOIs
StatePublished - Mar 29 2000

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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