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

David A. Jaeger, Dan Su, Abdullah Zafar, Barbora Piknova, Stephen (Steve) Hall

Research output: Contribution to journalArticle

26 Citations (Scopus)

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

Fingerprint

Regioselectivity
Cycloaddition Reaction
Surface-Active Agents
Iodides
Surface active agents
Cycloaddition
Micelles
Functional groups
Monolayers
Bromides
Ammonium Compounds
cyclohexene

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Regioselectivity control in Diels-Alder reactions of surfactant 1,3- dienes with surfactant dienophiles. / Jaeger, David A.; Su, Dan; Zafar, Abdullah; Piknova, Barbora; Hall, Stephen (Steve).

In: Journal of the American Chemical Society, Vol. 122, No. 12, 29.03.2000, p. 2749-2757.

Research output: Contribution to journalArticle

Jaeger, David A. ; Su, Dan ; Zafar, Abdullah ; Piknova, Barbora ; Hall, Stephen (Steve). / Regioselectivity control in Diels-Alder reactions of surfactant 1,3- dienes with surfactant dienophiles. In: Journal of the American Chemical Society. 2000 ; Vol. 122, No. 12. pp. 2749-2757.
@article{704fd077bb2b4d10b915a18eb017dd3b,
title = "Regioselectivity control in Diels-Alder reactions of surfactant 1,3- dienes with surfactant dienophiles",
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.",
author = "Jaeger, {David A.} and Dan Su and Abdullah Zafar and Barbora Piknova and Hall, {Stephen (Steve)}",
year = "2000",
month = "3",
day = "29",
doi = "10.1021/ja9940571",
language = "English (US)",
volume = "122",
pages = "2749--2757",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "12",

}

TY - JOUR

T1 - Regioselectivity control in Diels-Alder reactions of surfactant 1,3- dienes with surfactant dienophiles

AU - Jaeger, David A.

AU - Su, Dan

AU - Zafar, Abdullah

AU - Piknova, Barbora

AU - Hall, Stephen (Steve)

PY - 2000/3/29

Y1 - 2000/3/29

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=0034728649&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0034728649&partnerID=8YFLogxK

U2 - 10.1021/ja9940571

DO - 10.1021/ja9940571

M3 - Article

AN - SCOPUS:0034728649

VL - 122

SP - 2749

EP - 2757

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 12

ER -