Enantiodifferentiating photoisomerization of cyclooctene included and sensitized by aroyl-beta-cyclodextrins: A critical enantioselectivity control by substituents

	Enantiodifferentiating photoisomerization of cyclooctene included and sensitized by aroyl-beta-cyclodextrins: A critical enantioselectivity control by substituents
	Lu, RH ; Yang, C ; Cao, YJ ; Tong, LH ; Jiao, W ; Wada, T ; Wang, ZZ ; Mori, T ; Inoue, Y
刊名	JOURNAL OF ORGANIC CHEMISTRY
	2008
卷号	73 期号:19 页码:7695_7701
ISSN号	0022-3263
通讯作者	Lu, RH, China Agr Univ, Coll Sci, Dept Appl Chem, Beijing 100094, Peoples R China.
产权排序	2
中文摘要	A series of 6-O-benzoyl-beta-cyclodextrins (CDs) with methyl, methoxy, methoxycarbonyl, and bromo substituent(s) at the ortho-, meta-, and/or para-position(s) were synthesized as chiral sensitizing hosts for the use in supramolecular enantiodifferentiating photoisomerization of (Z)-cyclooctene (M) to its chiral (E)-isomer (1E). The complex stability constants (K-S) of the modified beta-CDs with 1Z in aqueous methanol solutions were highly sensitive to the substituent(s) introduced to the benzoate moiety, and the log K-S values decreased linearly with slightly different slopes with increasing methanol content. The enantiomeric excess (ee) of 1E obtained upon photosensitization with these hosts was a critical function of the size and position of the substituent, varying from almost zero to 46% ee. This indicates that even an apparently small structural difference between methyl and methoxy can critically affect the enantiodifferentiating photoisomerization of a guest included in the chiral cavity, probably through manipulation of both the orientation of ground-state 1Z and the subsequent rotational relaxation of excited 1Z inside the chiral cavity.
学科主题	Chemistry, Organic
收录类别	SCI
资助信息	Chinese Natural Science Foundation [20772120]; CAS-JSPS Exchange Program ; Japan Science and Technology Agency (ICORP and PRESTO)
语种	英语
WOS记录号	WOS:000259574700034
公开日期	2011-07-08
内容类型	期刊论文
源URL	[http://210.75.237.14/handle/351003/18091]
专题	成都生物研究所_天然产物研究
推荐引用方式 GB/T 7714	Lu, RH,Yang, C,Cao, YJ,et al. Enantiodifferentiating photoisomerization of cyclooctene included and sensitized by aroyl-beta-cyclodextrins: A critical enantioselectivity control by substituents[J]. JOURNAL OF ORGANIC CHEMISTRY,2008,73(19):7695_7701.
APA	Lu, RH.,Yang, C.,Cao, YJ.,Tong, LH.,Jiao, W.,...&Inoue, Y.(2008).Enantiodifferentiating photoisomerization of cyclooctene included and sensitized by aroyl-beta-cyclodextrins: A critical enantioselectivity control by substituents.JOURNAL OF ORGANIC CHEMISTRY,73(19),7695_7701.
MLA	Lu, RH,et al."Enantiodifferentiating photoisomerization of cyclooctene included and sensitized by aroyl-beta-cyclodextrins: A critical enantioselectivity control by substituents".JOURNAL OF ORGANIC CHEMISTRY 73.19(2008):7695_7701.