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

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

17 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
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
Externally published	Yes

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.

Funders	Funder number
Marie Curie Cofund Action
The Netherlands Organisation for Scientific Research
National Science Foundation
Howard Hughes Medical Institute
Northwestern University
Life Sciences Research Foundation
International Institute for Nanotechnology, Northwestern University
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
King Abdulaziz City for Science and Technology

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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.",

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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

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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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