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Dumbbell-Type Fullerene-Steroid Hybrids: A Join Experimental and Theoretical Investigation for Conformational, Configurational, and Circular Dichroism Assignments.

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Title: Dumbbell-Type Fullerene-Steroid Hybrids: A Join Experimental and Theoretical Investigation for Conformational, Configurational, and Circular Dichroism Assignments.
Authors: Ruíz, Alberto1, Morera-Boado, Cercis2, Almagro, Luis1, Coro, Julieta1, Maroto, Enrique E.3, Herranz, María Ángeles3, Filippone, Salvatore3, Molero, Dolores4, Martínez-Álvarez, Roberto3, de la Vega, José M. Garcia5, Suárez, Margarita1 msuarez@fq.uh.cu, Martín, Nazario3 nazmar@quim.ucm.es
Source: Journal of Organic Chemistry. 4/18/2014, Vol. 79 Issue 8, p3473-3486. 14p.
Subjects: Fullerenes, Steroids, Dichroism, Ring formation (Chemistry), Cyclopropanation
Abstract: New [60]fullerene-steroid conjugates (4-6) have been synthesized by 1,3-dipolar cycloaddition and Bingel-Hirsch cyclopropanation reactions from suitably functionalized epiandrosterone and [60]fullerene. Since a new stereocenter is created in the formation of the Prato monoaduct, two different diastereomers were isolated by HPLC (4, 5) whose absolute configurations were assigned according to the highly reliable "sector rule" on fullerenes. A further reaction of the malonate-containing diastereomer 5 with a second C60 molecule has afforded dumbbell fullerene 6 in which the two fullerene units are covalently connected through an epiandrosterone moiety. The new compounds have been spectroscopically characterized and their redox potentials, determined by cyclic voltametry, reveal three reversible reduction waves for hybrids 4 and 5, whereas these signals are split in dumbbell 6. Theoretical calculations at semiempirical (AM1) and single point B3LYP/6-31G(d) levels have predicted the most stable conformations for the hybrid compounds (4-6), showing the importance of the chlorine atom on the D ring of the steroid. Furthermore, TDDFT calculations have allowed assignments of the experimentally determined circular dichroism (CD) of the [60]fullerene-steroid hybrids based on the sign and position of the Cotton effects, despite the exceptionally large systems under study. [ABSTRACT FROM AUTHOR]
Copyright of Journal of Organic Chemistry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)
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  Data: Dumbbell-Type Fullerene-Steroid Hybrids: A Join Experimental and Theoretical Investigation for Conformational, Configurational, and Circular Dichroism Assignments.
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  Data: <searchLink fieldCode="AR" term="%22Ruíz%2C+Alberto%22">Ruíz, Alberto</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Morera-Boado%2C+Cercis%22">Morera-Boado, Cercis</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Almagro%2C+Luis%22">Almagro, Luis</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Coro%2C+Julieta%22">Coro, Julieta</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Maroto%2C+Enrique+E%2E%22">Maroto, Enrique E.</searchLink><relatesTo>3</relatesTo><br /><searchLink fieldCode="AR" term="%22Herranz%2C+María+Ángeles%22">Herranz, María Ángeles</searchLink><relatesTo>3</relatesTo><br /><searchLink fieldCode="AR" term="%22Filippone%2C+Salvatore%22">Filippone, Salvatore</searchLink><relatesTo>3</relatesTo><br /><searchLink fieldCode="AR" term="%22Molero%2C+Dolores%22">Molero, Dolores</searchLink><relatesTo>4</relatesTo><br /><searchLink fieldCode="AR" term="%22Martínez-Álvarez%2C+Roberto%22">Martínez-Álvarez, Roberto</searchLink><relatesTo>3</relatesTo><br /><searchLink fieldCode="AR" term="%22de+la+Vega%2C+José+M%2E+Garcia%22">de la Vega, José M. Garcia</searchLink><relatesTo>5</relatesTo><br /><searchLink fieldCode="AR" term="%22Suárez%2C+Margarita%22">Suárez, Margarita</searchLink><relatesTo>1</relatesTo><i> msuarez@fq.uh.cu</i><br /><searchLink fieldCode="AR" term="%22Martín%2C+Nazario%22">Martín, Nazario</searchLink><relatesTo>3</relatesTo><i> nazmar@quim.ucm.es</i>
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  Data: <searchLink fieldCode="JN" term="%22Journal+of+Organic+Chemistry%22">Journal of Organic Chemistry</searchLink>. 4/18/2014, Vol. 79 Issue 8, p3473-3486. 14p.
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  Data: New [60]fullerene-steroid conjugates (4-6) have been synthesized by 1,3-dipolar cycloaddition and Bingel-Hirsch cyclopropanation reactions from suitably functionalized epiandrosterone and [60]fullerene. Since a new stereocenter is created in the formation of the Prato monoaduct, two different diastereomers were isolated by HPLC (4, 5) whose absolute configurations were assigned according to the highly reliable "sector rule" on fullerenes. A further reaction of the malonate-containing diastereomer 5 with a second C60 molecule has afforded dumbbell fullerene 6 in which the two fullerene units are covalently connected through an epiandrosterone moiety. The new compounds have been spectroscopically characterized and their redox potentials, determined by cyclic voltametry, reveal three reversible reduction waves for hybrids 4 and 5, whereas these signals are split in dumbbell 6. Theoretical calculations at semiempirical (AM1) and single point B3LYP/6-31G(d) levels have predicted the most stable conformations for the hybrid compounds (4-6), showing the importance of the chlorine atom on the D ring of the steroid. Furthermore, TDDFT calculations have allowed assignments of the experimentally determined circular dichroism (CD) of the [60]fullerene-steroid hybrids based on the sign and position of the Cotton effects, despite the exceptionally large systems under study. [ABSTRACT FROM AUTHOR]
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  Data: <i>Copyright of Journal of Organic Chemistry is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.)
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        Value: 10.1021/jo500178t
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      – Code: eng
        Text: English
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        PageCount: 14
        StartPage: 3473
    Subjects:
      – SubjectFull: Fullerenes
        Type: general
      – SubjectFull: Steroids
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      – SubjectFull: Dichroism
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      – SubjectFull: Ring formation (Chemistry)
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      – SubjectFull: Cyclopropanation
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      – TitleFull: Dumbbell-Type Fullerene-Steroid Hybrids: A Join Experimental and Theoretical Investigation for Conformational, Configurational, and Circular Dichroism Assignments.
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              Text: 4/18/2014
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