Tetraphenylporphine-sensitized photooxygenation of (E,E)- and (E,Z)-1- aryl-1,3-pentadienes generating cis-endoperoxides

Jiro Motoyoshiya, Yasuyuki Okuda, Ichiro Matsuoka, Sadao Hayashi, Yutaka Takaguchi, Hiromu Aoyama

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

Photooxygenation of either (E,E)- or (E,Z)-1-aryl-1,3-pentadienes (1a- c) sensitized with tetraphenylporphine (TPP) in benzene gave almost all cis- endoperoxides (2a-c) (cis-3-aryl-6-methyl-1,2-dioxacyclohex-4-enes) in good yields. A time course study of photooxygenation of (E,Z)-rich dienes measured by 1H NMR showed that singlet oxygen added exclusively to (E,E)-dienes converted from (E,Z)-dienes by photoinduced isomerization, and both rates increased when electron-donating groups were attached to the aryl group. A concerted [4 + 2] cycloaddition mechanism is suggested by the exclusive formation of cis-endoperoxides from (E,E)-dienes, despite the small energy difference between cis- and trans-endoperoxides calculated by ab initio methods. Some experiments were made to explore the observed isomerization.

Original languageEnglish
Pages (from-to)493-497
Number of pages5
JournalJournal of Organic Chemistry
Volume64
Issue number2
DOIs
Publication statusPublished - Jan 22 1999
Externally publishedYes

Fingerprint

Isomerization
Singlet Oxygen
Time and motion study
Cycloaddition
Benzene
Nuclear magnetic resonance
Electrons
Experiments
1,3-pentadiene
tetraphenylporphine

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Tetraphenylporphine-sensitized photooxygenation of (E,E)- and (E,Z)-1- aryl-1,3-pentadienes generating cis-endoperoxides. / Motoyoshiya, Jiro; Okuda, Yasuyuki; Matsuoka, Ichiro; Hayashi, Sadao; Takaguchi, Yutaka; Aoyama, Hiromu.

In: Journal of Organic Chemistry, Vol. 64, No. 2, 22.01.1999, p. 493-497.

Research output: Contribution to journalArticle

Motoyoshiya, Jiro ; Okuda, Yasuyuki ; Matsuoka, Ichiro ; Hayashi, Sadao ; Takaguchi, Yutaka ; Aoyama, Hiromu. / Tetraphenylporphine-sensitized photooxygenation of (E,E)- and (E,Z)-1- aryl-1,3-pentadienes generating cis-endoperoxides. In: Journal of Organic Chemistry. 1999 ; Vol. 64, No. 2. pp. 493-497.
@article{ee5e782d99b04237929b3259ffd464b2,
title = "Tetraphenylporphine-sensitized photooxygenation of (E,E)- and (E,Z)-1- aryl-1,3-pentadienes generating cis-endoperoxides",
abstract = "Photooxygenation of either (E,E)- or (E,Z)-1-aryl-1,3-pentadienes (1a- c) sensitized with tetraphenylporphine (TPP) in benzene gave almost all cis- endoperoxides (2a-c) (cis-3-aryl-6-methyl-1,2-dioxacyclohex-4-enes) in good yields. A time course study of photooxygenation of (E,Z)-rich dienes measured by 1H NMR showed that singlet oxygen added exclusively to (E,E)-dienes converted from (E,Z)-dienes by photoinduced isomerization, and both rates increased when electron-donating groups were attached to the aryl group. A concerted [4 + 2] cycloaddition mechanism is suggested by the exclusive formation of cis-endoperoxides from (E,E)-dienes, despite the small energy difference between cis- and trans-endoperoxides calculated by ab initio methods. Some experiments were made to explore the observed isomerization.",
author = "Jiro Motoyoshiya and Yasuyuki Okuda and Ichiro Matsuoka and Sadao Hayashi and Yutaka Takaguchi and Hiromu Aoyama",
year = "1999",
month = "1",
day = "22",
doi = "10.1021/jo981506r",
language = "English",
volume = "64",
pages = "493--497",
journal = "Journal of Organic Chemistry",
issn = "0022-3263",
publisher = "American Chemical Society",
number = "2",

}

TY - JOUR

T1 - Tetraphenylporphine-sensitized photooxygenation of (E,E)- and (E,Z)-1- aryl-1,3-pentadienes generating cis-endoperoxides

AU - Motoyoshiya, Jiro

AU - Okuda, Yasuyuki

AU - Matsuoka, Ichiro

AU - Hayashi, Sadao

AU - Takaguchi, Yutaka

AU - Aoyama, Hiromu

PY - 1999/1/22

Y1 - 1999/1/22

N2 - Photooxygenation of either (E,E)- or (E,Z)-1-aryl-1,3-pentadienes (1a- c) sensitized with tetraphenylporphine (TPP) in benzene gave almost all cis- endoperoxides (2a-c) (cis-3-aryl-6-methyl-1,2-dioxacyclohex-4-enes) in good yields. A time course study of photooxygenation of (E,Z)-rich dienes measured by 1H NMR showed that singlet oxygen added exclusively to (E,E)-dienes converted from (E,Z)-dienes by photoinduced isomerization, and both rates increased when electron-donating groups were attached to the aryl group. A concerted [4 + 2] cycloaddition mechanism is suggested by the exclusive formation of cis-endoperoxides from (E,E)-dienes, despite the small energy difference between cis- and trans-endoperoxides calculated by ab initio methods. Some experiments were made to explore the observed isomerization.

AB - Photooxygenation of either (E,E)- or (E,Z)-1-aryl-1,3-pentadienes (1a- c) sensitized with tetraphenylporphine (TPP) in benzene gave almost all cis- endoperoxides (2a-c) (cis-3-aryl-6-methyl-1,2-dioxacyclohex-4-enes) in good yields. A time course study of photooxygenation of (E,Z)-rich dienes measured by 1H NMR showed that singlet oxygen added exclusively to (E,E)-dienes converted from (E,Z)-dienes by photoinduced isomerization, and both rates increased when electron-donating groups were attached to the aryl group. A concerted [4 + 2] cycloaddition mechanism is suggested by the exclusive formation of cis-endoperoxides from (E,E)-dienes, despite the small energy difference between cis- and trans-endoperoxides calculated by ab initio methods. Some experiments were made to explore the observed isomerization.

UR - http://www.scopus.com/inward/record.url?scp=0033593514&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0033593514&partnerID=8YFLogxK

U2 - 10.1021/jo981506r

DO - 10.1021/jo981506r

M3 - Article

AN - SCOPUS:0033593514

VL - 64

SP - 493

EP - 497

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 2

ER -