Sensitized Photooxygenation of Cholesterol and Pseudocholesterol Derivatives via Singlet Oxygen 英文参考文献.docVIP

Molecules 2001, 6, 52-60 molecules ISSN 1420-3049 ? 2001 by MDPI Sensitized Photooxygenation of Cholesterol and Pseudo- cholesterol Derivatives via Singlet Oxygen Wu Shuping 1, Jiang Zhiqin 2, *, Li Heting 1, Yang Li 2 and Zeng Daixun2 1 Research Laboratory of Photochemistry, Tongji University, Shanghai 200092, P. R. China. Tel.: +86 21 Fax: +86 21 E-mail: jzqcdtju@ 2 National Laboratory of Applied Organic Chemistry at Lanzhou University, Lanzhou 730000, P. R. China. *Author to whom correspondence should be addressed. E-mail: jzqcdtju@ Received: 30 September 1998; in revised form 4 September 2000 / Accepted: 19 September 2000 / Published: 16 January 2001 Abstract: 3-Substituted cholesterols and 7-substituted pseudocholesterols undergo a facile photooxygenation sensitized by 9, 10-dicyanoanthracene (DCA) and lumiflavin (LF) to give similar, oppositely-positioned enol derivatives. Both steroids showed the same reaction pattern associated with the endocyclic 5- and 4-olefin units, respectively. The reaction was proposed to proceed via the ene reaction of singlet oxygen and subsequent rearrangement of the initially formed 5α-hydroperoxides. Keywords: Cholesterol and pseudocholesterol derivatives, ene reaction of singlet oxygen, photochemical damage. Introduction Photochemical damage of biological molecules by reactive oxygen species (1O2, O2-· , HO· , RO· , [O] etc.) have received increasing attention recently [1,2]. Studies indicate that a number of biological pigments e.g. hematoporphyrin, riboflavin and chlorophyll etc. can readily sensitize the photooxygenation of ?5-steroids such as cholesterol, which may cause some diseases or damage to biological organs. One of the effects found was an increase the brittleness of the cell membrane, which leads to hemolysis [3]. It was also verified that oxygen can affect the synthesis and metabolism of  Molecules 2001, 6 53 pr