Diels-Alder reactions of 2,3-bis-(phenylthio)-1,3-butadiene: X-ray and NMR structural investigations ofcis andtrans-1,2-bis-(phenylthio)-4,5-dimethoxycarbonyl-1-cyclohexene

Jaeger, David A.; Wang, Jinkang

doi:10.1007/bf01185543

Cited by 4 publications

(10 citation statements)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A previous study 5a,b included the cycloaddition of surfactant dienophile 2b with surfactant 1,3-diene 20 , which was generated in situ at 100 °C by the thermal extrusion of SO 2 from precursor surfactant 21 . Even though the lengths of the tethers between the quaternary ammonium headgroups and dienophile groups of 1b and 20 are comparable, the 15b / 16b ratio of 6.6:1 obtained from 1b and 2b in the present study at 25 °C is more than twice the 22 / 23 ratio of 3.0:1 obtained from 20 and 2b at 100 °C. 5a,b The greater regioselectivity obtained with the former pair is attributed at least in part to the expected greater organizational abilities of micelles at low compared to high temperatures. Also, 1b , unlike 20 , does not contain aromatic groups, which can associate with quaternary ammonium headgroups .…”

Section: Resultscontrasting

confidence: 62%

“…The synthesis of amino diesters 14 and surfactant dienophile 2a is outlined in Scheme ; 2b was prepared previously by another pathway. 5a,b The reaction of maleic anhydride with HO(CH 2 ) 2 NMe 2 or 10 gave half esters 13 , which were then esterified to give 14 . Quaternization of 14a with MeI gave 2a .…”

Section: Resultsmentioning

confidence: 99%

“…By surface tensiometry (du Noüy ring) the critical micelle concentrations (cmcs) of 1a , 1b , 2a , and 2b in H 2 O at 25 °C are 0.75 × 10 -4 , 1.0 × 10 -4 , 0.30 × 10 -3 , and 4.4 × 10 -3 M, 5a,b respectively. The Krafft temperatures in H 2 O of 1a , 1b , and 2b are ≤25 °C, and that of 2a is ca.…”

Section: Resultsmentioning

confidence: 99%

“…B. F. N. Engberts and co-workers have recently reported a million-fold rate acceleration of a Diels−Alder reaction resulting from combined Lewis acid and micellar catalysis in H 2 O,3a and enhanced enantioselectivity in a chiral Lewis acid-catalyzed Diels−Alder reaction in H 2 O 3b. On the other hand, there have been only a few studies of the ability of interfacial orientational effects within aqueous surfactant-based media to control the regioselectivity of Diels−Alder reactions. , In one involving a surfactant 1,3-diene and a neutral nonsurfactant dienophile, orientational effects were not strong enough to overcome the reaction's intrinsically preferred regiochemistry . In another study involving a different surfactant 1,3-diene and surfactant dienophiles, modest regioselectivity was obtained .…”

Section: Introductionmentioning

confidence: 99%

“…On the other hand, there have been only a few studies of the ability of interfacial orientational effects within aqueous surfactant-based media to control the regioselectivity of Diels−Alder reactions. , In one involving a surfactant 1,3-diene and a neutral nonsurfactant dienophile, orientational effects were not strong enough to overcome the reaction's intrinsically preferred regiochemistry . In another study involving a different surfactant 1,3-diene and surfactant dienophiles, modest regioselectivity was obtained . There have been a few reports of the effect on regiochemistry of performing Diels−Alder reactions in H 2 O alone …”

Section: Introductionmentioning

confidence: 99%

See 4 more Smart Citations

Regioselectivity Control in Diels−Alder Reactions of Surfactant 1,3-Dienes with Surfactant Dienophiles

Jaeger¹,

Su²,

Zafar³

et al. 2000

J. Am. Chem. Soc.

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Section: Resultscontrasting

confidence: 62%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Regioselectivity Control in Diels−Alder Reactions of Surfactant 1,3-Dienes with Surfactant Dienophiles

Jaeger¹,

Su²,

Zafar³

et al. 2000

J. Am. Chem. Soc.

Self Cite

View full text Add to dashboard Cite

show abstract

Extrusion Reactions Affording Aromatic Systems, Dienes and Polyenes

Guziec

2022

Organic Reactions

View full text Add to dashboard Cite

Extrusion reactions may be defined as chemical reactions in which an atom or small molecular fragment Y connected to two other atoms W and Z is lost from a molecule, leading to a product in which W becomes directly bonded to Z. Cheletropic reactions that afford aromatic or conjugated π systems by loss of a stable atomic or molecular fragment have also been classified as extrusion reactions. Typically, the fragments liberated in these reactions are small, stable inorganic molecules or atoms such as carbon monoxide, carbon dioxide, sulfur, sulfur monoxide, sulfur dioxide, selenium, tellurium, oxygen and nitrogen. This chapter primarily deals with the synthesis of arenes, heterocycles, 1,3‐dienes and polyenes using such extrusion processes. The utility of these reactions in the synthesis of sterically hindered molecules, dendrimers, pheromones, and other natural products are highlighted. The use of extrusion reactions for the “Click and Release” approach in drug development is also introduced.

show abstract

High regioselectivity in the Diels-Alder reaction of a surfactant 1,3-diene with a surfactant dienophile resulting from a short tether between their functional groups and head groups

Su¹,

Jaeger²

1999

Tetrahedron Letters

View full text Add to dashboard Cite

Diels-Alder reactions of 2,3-bis-(phenylthio)-1,3-butadiene: X-ray and NMR structural investigations ofcis andtrans-1,2-bis-(phenylthio)-4,5-dimethoxycarbonyl-1-cyclohexene

Cited by 4 publications

References 14 publications

Regioselectivity Control in Diels−Alder Reactions of Surfactant 1,3-Dienes with Surfactant Dienophiles

Regioselectivity Control in Diels−Alder Reactions of Surfactant 1,3-Dienes with Surfactant Dienophiles

Extrusion Reactions Affording Aromatic Systems, Dienes and Polyenes

High regioselectivity in the Diels-Alder reaction of a surfactant 1,3-diene with a surfactant dienophile resulting from a short tether between their functional groups and head groups

Contact Info

Product

Resources

About