TY - JOUR
T1 - Sensitized Photooxygenation of 6-Heteroatom-Substituted Fulvenes
T2 - Primary Products and Their Chemical Transformations
AU - Zhang, Xiaojun
AU - Lin, Feng
AU - Foote, Christopher S.
PY - 1995/3/1
Y1 - 1995/3/1
N2 - Sensitized photooxygenation of 6, 6-diethoxyfulvene (1) and 6, 6-(ethylenedithio)fulvene (9) at —78 °C afforded diethoxyfulvene endoperoxide 2 and (ethylenedithio)fulvene endoperoxide 10, respectively, as primary products. Further irradiation resulted in formation of the novel bisperoxides 3 and 11 from [2 + 2] cycloaddition of 1O2 to the exocyclic double bond of the corresponding endoperoxides. The initial endoperoxides were characterized by NMR at low temperature and underwent a variety of chemical transformations to give highly oxygenated cyclopentane derivatives. In contrast, photooxygenation of 6, 6-dipiperidinofulvene (16) and 6-(dimethylamino)fulvene (17) did not lead to chemical reaction; these compounds physically quench 1O2 with rate constants on the order of 108 M-1 s-1.
AB - Sensitized photooxygenation of 6, 6-diethoxyfulvene (1) and 6, 6-(ethylenedithio)fulvene (9) at —78 °C afforded diethoxyfulvene endoperoxide 2 and (ethylenedithio)fulvene endoperoxide 10, respectively, as primary products. Further irradiation resulted in formation of the novel bisperoxides 3 and 11 from [2 + 2] cycloaddition of 1O2 to the exocyclic double bond of the corresponding endoperoxides. The initial endoperoxides were characterized by NMR at low temperature and underwent a variety of chemical transformations to give highly oxygenated cyclopentane derivatives. In contrast, photooxygenation of 6, 6-dipiperidinofulvene (16) and 6-(dimethylamino)fulvene (17) did not lead to chemical reaction; these compounds physically quench 1O2 with rate constants on the order of 108 M-1 s-1.
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U2 - 10.1021/jo00110a043
DO - 10.1021/jo00110a043
M3 - Article
AN - SCOPUS:0343359365
SN - 0022-3263
VL - 60
SP - 1333
EP - 1338
JO - Journal of Organic Chemistry
JF - Journal of Organic Chemistry
IS - 5
ER -