Regiochemistry of twofold additions to [6,6] bonds in C60: Influence of the addend-independent cage distortion in 1,2-monoadducts

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Details zur Publikation

Autorinnen und Autoren: Djojo F, Herzog A, Lamparth I, Hampel F, Hirsch A
Zeitschrift: Chemistry - A European Journal
Verlag: Wiley-VCH Verlag
Jahr der Veröffentlichung: 1996
Band: 2
Heftnummer: 12
Seitenbereich: 1537-1547
ISSN: 0947-6539


Abstract


Three series of regioisomeric bisadducts of C, namely, C (anisyl) and the mixed systems C(anisyl) -(COOEt) and C(COOEt)(NCOOEt), were synthesized starting from the 1,2-monoadducts C(COOEt) (1), C-(anisyl) (2), and C (NCOOEt) (4) by using the Bingel and Bamford-Stevens reactions, and nitrene additions. In the case of C(COOEt)(NCOOEt) the complete series of nine possible regioisomers were isolated for the first time. For steric reasons the cis-1 isomers of C(anisyl) and C(anisyl)(COOEt) were not formed. The transannular [6,6] bonds in the cis-1 isomer 42 of C(COOEt) (NCOOEt) are closed. The properties and regioselectivities of formation of these bisadducts and their monoadduct precursors were compared with those of the series C-(COOEt) and C (NCOOEt), which we synthesized previously. In the additions to 1, 2, and 4 the preferred positions of attack are e and trans-3 for sterically demanding addends (e.g., combinations of C(anisyl) and C(COOEt)) and cis-1, e, and trans-3 for sterically less demanding addends (e.g., combinations of N(COOEt) and C(COOEt)). A detailed analysis of the MO structures, the experimental and calculated geometries of monoadduct precursors, and the stabilities of reaction products leads to the conclusion that the addend-independent cage distortion itself is responsible for the observed regioselectivities of bisadduct formations. © VCH Verlagsgesellschaft mbH, 1996.



FAU-Autorinnen und Autoren / FAU-Herausgeberinnen und Herausgeber

Hampel, Frank Dr.
Lehrstuhl für Organische Chemie I
Hirsch, Andreas Prof. Dr.
Lehrstuhl für Organische Chemie II


Zitierweisen

APA:
Djojo, F., Herzog, A., Lamparth, I., Hampel, F., & Hirsch, A. (1996). Regiochemistry of twofold additions to [6,6] bonds in C60: Influence of the addend-independent cage distortion in 1,2-monoadducts. Chemistry - A European Journal, 2(12), 1537-1547. https://dx.doi.org/10.1002/chem.19960021211

MLA:
Djojo, Francis, et al. "Regiochemistry of twofold additions to [6,6] bonds in C60: Influence of the addend-independent cage distortion in 1,2-monoadducts." Chemistry - A European Journal 2.12 (1996): 1537-1547.

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