Cooperative Reactivity in an Extended-Viologen-Based Cyclophane

Edward J. Dale; Daniel P. Ferris; Nicolaas A. Vermeulen; James J. Henkelis; Ilja Popovs; Michal Juríček; Jonathan C. Barnes; Severin T. Schneebeli; J. Fraser Stoddart

doi:10.1021/jacs.6b01368

Cooperative Reactivity in an Extended-Viologen-Based Cyclophane

Edward J. Dale, Daniel P. Ferris, Nicolaas A. Vermeulen, James J. Henkelis, Ilja Popovs, Michal Juríček, Jonathan C. Barnes, Severin T. Schneebeli^*, J. Fraser Stoddart

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

16 Scopus citations

Abstract

A tetracationic pyridinium-based cyclophane with a box-like geometry, incorporating two juxtaposed alkyne functions, has been synthesized. The triple bonds are reactive through cycloadditions toward dienes and azides, promoted by the electron-withdrawing nature of the pyridinium rings, as well as by the strain inherent in the cyclophane. The cycloadditions proceeded in high yields, with the cyclophane reacting faster than its acyclic analogue. While the cyclophane contains two reactive triple bonds, there is no evidence for a stable monofunctional intermediate-only starting material and the difunctional product have been detected by ¹H NMR spectroscopy. Molecular modeling of the energy landscape reveals a lower barrier for the kinetically favored second cycloaddition compared with the first one. This situation results in tandem cascading reactions within rigid cyclophanes, where reactions at a first triple bond induce increased reactivity at a distal second alkyne.

Original language	English (US)
Pages (from-to)	3667-3670
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	138
Issue number	11
DOIs	https://doi.org/10.1021/jacs.6b01368
State	Published - Mar 23 2016

Funding

ACKNOWLEDGMENTS: This research was conducted as part of the Joint Center of Excellence in Integrated Nanosystems at King Abdulaziz City for Science and Technology (KACST) and Northwestern University (NU). E.J.D. is supported by a Graduate Research Fellowship from the National Science Foundation and a Ryan Fellowship through the NU International Institute for Nanotechnology. M.J. gratefully acknowledges The Netherlands Organisation for Scientific Research (NWO) and the Marie Curie Cofund Action (Rubicon Fellowship) for financial support. J.C.B. is supported by a Howard Hughes Medical Institute Postdoctoral Fellowship through the Life Sciences Research Foundation.

ASJC Scopus subject areas

General Chemistry
Biochemistry
Catalysis
Colloid and Surface Chemistry

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10.1021/jacs.6b01368

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title = "Cooperative Reactivity in an Extended-Viologen-Based Cyclophane",

abstract = "A tetracationic pyridinium-based cyclophane with a box-like geometry, incorporating two juxtaposed alkyne functions, has been synthesized. The triple bonds are reactive through cycloadditions toward dienes and azides, promoted by the electron-withdrawing nature of the pyridinium rings, as well as by the strain inherent in the cyclophane. The cycloadditions proceeded in high yields, with the cyclophane reacting faster than its acyclic analogue. While the cyclophane contains two reactive triple bonds, there is no evidence for a stable monofunctional intermediate-only starting material and the difunctional product have been detected by 1H NMR spectroscopy. Molecular modeling of the energy landscape reveals a lower barrier for the kinetically favored second cycloaddition compared with the first one. This situation results in tandem cascading reactions within rigid cyclophanes, where reactions at a first triple bond induce increased reactivity at a distal second alkyne.",

author = "Dale, {Edward J.} and Ferris, {Daniel P.} and Vermeulen, {Nicolaas A.} and Henkelis, {James J.} and Ilja Popovs and Michal Jur{\'i}{\v c}ek and Barnes, {Jonathan C.} and Schneebeli, {Severin T.} and Stoddart, {J. Fraser}",

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AU - Dale, Edward J.

AU - Ferris, Daniel P.

AU - Vermeulen, Nicolaas A.

AU - Henkelis, James J.

AU - Popovs, Ilja

AU - Juríček, Michal

AU - Barnes, Jonathan C.

AU - Schneebeli, Severin T.

AU - Stoddart, J. Fraser

PY - 2016/3/23

Y1 - 2016/3/23

N2 - A tetracationic pyridinium-based cyclophane with a box-like geometry, incorporating two juxtaposed alkyne functions, has been synthesized. The triple bonds are reactive through cycloadditions toward dienes and azides, promoted by the electron-withdrawing nature of the pyridinium rings, as well as by the strain inherent in the cyclophane. The cycloadditions proceeded in high yields, with the cyclophane reacting faster than its acyclic analogue. While the cyclophane contains two reactive triple bonds, there is no evidence for a stable monofunctional intermediate-only starting material and the difunctional product have been detected by 1H NMR spectroscopy. Molecular modeling of the energy landscape reveals a lower barrier for the kinetically favored second cycloaddition compared with the first one. This situation results in tandem cascading reactions within rigid cyclophanes, where reactions at a first triple bond induce increased reactivity at a distal second alkyne.

AB - A tetracationic pyridinium-based cyclophane with a box-like geometry, incorporating two juxtaposed alkyne functions, has been synthesized. The triple bonds are reactive through cycloadditions toward dienes and azides, promoted by the electron-withdrawing nature of the pyridinium rings, as well as by the strain inherent in the cyclophane. The cycloadditions proceeded in high yields, with the cyclophane reacting faster than its acyclic analogue. While the cyclophane contains two reactive triple bonds, there is no evidence for a stable monofunctional intermediate-only starting material and the difunctional product have been detected by 1H NMR spectroscopy. Molecular modeling of the energy landscape reveals a lower barrier for the kinetically favored second cycloaddition compared with the first one. This situation results in tandem cascading reactions within rigid cyclophanes, where reactions at a first triple bond induce increased reactivity at a distal second alkyne.

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Cooperative Reactivity in an Extended-Viologen-Based Cyclophane

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CCDC 1451537: Experimental Crystal Structure Determination

CCDC 1451539: Experimental Crystal Structure Determination

CCDC 1451536: Experimental Crystal Structure Determination

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Cooperative Reactivity in an Extended-Viologen-Based Cyclophane

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CCDC 1451537: Experimental Crystal Structure Determination

CCDC 1451539: Experimental Crystal Structure Determination

CCDC 1451536: Experimental Crystal Structure Determination

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