Electron-Transfer-Induced Reorganization of Bicyclo[6.1.0]nonatriene and Derivatives

Heinz D. Roth; Marcia L. Schilling; Christopher J. Abelt; Tsutomu Miyashi; Yasutake Takahashi; Akinori Konno; Toshio Mukai

doi:10.1021/ja00223a036

Electron-Transfer-Induced Reorganization of Bicyclo[6.1.0]nonatriene and Derivatives

Heinz D. Roth, Marcia L. Schilling, Christopher J. Abelt, Tsutomu Miyashi, Yasutake Takahashi, Akinori Konno, Toshio Mukai

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

10 Scopus citations

Abstract

The radical cations of bicyclo[6.1.01nonatriene (1a) and several derivatives (1b-f) have been generated by photoinduced electron transfer in solution. The radical cation 3a, derived from the parent, has a weakened cyclopropane bond with spin (and charge) density at C₁ and C₈. Electron return in singlet pairs regenerates la, whereas triplet recombination gives rise to cyclononatetraene (6). Electron-withdrawing substituents at C₉(Cl, 1c) cause spin and charge to be restricted to the triene moiety. The 9,9-diphenyl derivative 1d undergoes electron-transfer-induced rearrangement to 7-(β,β-diphenylethenyl)-cycloheptatriene, whereas the spirofluorene derivative 1f is converted to a barbaralane derivative 9f. The homoaromatic radical cation 10f is suggested as an intermediate in this remarkable rearrangement.

Original language	English (US)
Pages (from-to)	5130-5136
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	110
Issue number	15
DOIs	https://doi.org/10.1021/ja00223a036
State	Published - Jul 1988
Externally published	Yes

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja00223a036

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title = "Electron-Transfer-Induced Reorganization of Bicyclo[6.1.0]nonatriene and Derivatives",

abstract = "The radical cations of bicyclo[6.1.01nonatriene (1a) and several derivatives (1b-f) have been generated by photoinduced electron transfer in solution. The radical cation 3a, derived from the parent, has a weakened cyclopropane bond with spin (and charge) density at C1 and C8. Electron return in singlet pairs regenerates la, whereas triplet recombination gives rise to cyclononatetraene (6). Electron-withdrawing substituents at C9(Cl, 1c) cause spin and charge to be restricted to the triene moiety. The 9,9-diphenyl derivative 1d undergoes electron-transfer-induced rearrangement to 7-(β,β-diphenylethenyl)-cycloheptatriene, whereas the spirofluorene derivative 1f is converted to a barbaralane derivative 9f. The homoaromatic radical cation 10f is suggested as an intermediate in this remarkable rearrangement.",

author = "Roth, {Heinz D.} and Schilling, {Marcia L.} and Abelt, {Christopher J.} and Tsutomu Miyashi and Yasutake Takahashi and Akinori Konno and Toshio Mukai",

year = "1988",

month = jul,

doi = "10.1021/ja00223a036",

language = "English (US)",

volume = "110",

pages = "5130--5136",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

number = "15",

}

TY - JOUR

T1 - Electron-Transfer-Induced Reorganization of Bicyclo[6.1.0]nonatriene and Derivatives

AU - Roth, Heinz D.

AU - Schilling, Marcia L.

AU - Abelt, Christopher J.

AU - Miyashi, Tsutomu

AU - Takahashi, Yasutake

AU - Konno, Akinori

AU - Mukai, Toshio

PY - 1988/7

Y1 - 1988/7

N2 - The radical cations of bicyclo[6.1.01nonatriene (1a) and several derivatives (1b-f) have been generated by photoinduced electron transfer in solution. The radical cation 3a, derived from the parent, has a weakened cyclopropane bond with spin (and charge) density at C1 and C8. Electron return in singlet pairs regenerates la, whereas triplet recombination gives rise to cyclononatetraene (6). Electron-withdrawing substituents at C9(Cl, 1c) cause spin and charge to be restricted to the triene moiety. The 9,9-diphenyl derivative 1d undergoes electron-transfer-induced rearrangement to 7-(β,β-diphenylethenyl)-cycloheptatriene, whereas the spirofluorene derivative 1f is converted to a barbaralane derivative 9f. The homoaromatic radical cation 10f is suggested as an intermediate in this remarkable rearrangement.

AB - The radical cations of bicyclo[6.1.01nonatriene (1a) and several derivatives (1b-f) have been generated by photoinduced electron transfer in solution. The radical cation 3a, derived from the parent, has a weakened cyclopropane bond with spin (and charge) density at C1 and C8. Electron return in singlet pairs regenerates la, whereas triplet recombination gives rise to cyclononatetraene (6). Electron-withdrawing substituents at C9(Cl, 1c) cause spin and charge to be restricted to the triene moiety. The 9,9-diphenyl derivative 1d undergoes electron-transfer-induced rearrangement to 7-(β,β-diphenylethenyl)-cycloheptatriene, whereas the spirofluorene derivative 1f is converted to a barbaralane derivative 9f. The homoaromatic radical cation 10f is suggested as an intermediate in this remarkable rearrangement.

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DO - 10.1021/ja00223a036

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 15

ER -

Electron-Transfer-Induced Reorganization of Bicyclo[6.1.0]nonatriene and Derivatives

Abstract

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