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Please use this identifier to cite or link to this item: http://dspace.library.iitb.ac.in/jspui/handle/10054/3822

Title: Enhanced diastereoselectivity via confinement: Diastereoselective photoisomerization of 2,3-diphenyl-1-benzoylcyclopropane derivatives within zeolites
Authors: SIVAGURU, J
SUNOJ, RB
WADA, T
ORIGANE, Y
INOUE, Y
RAMAMURTHY, V
Keywords: mechanistic organic photochemistry
cation-pi interactions
gas-phase
cyclopropyl ketones
rotational barriers
amino-acid
1,2-diarylcyclopropanes
n,n-dimethylformamide
rearrangements
complexes
Issue Date: 2004
Publisher: AMER CHEMICAL SOC
Citation: JOURNAL OF ORGANIC CHEMISTRY, 69(17), 5528-5536
Abstract: Photochemistry of optically pure trans-2,3-diphenyl-1-benzoylcyclopropane has been examined in isotropic solution and within zeolites. Results suggest that it isomerizes by cleavage of either the C-1-C-2 or C-1-C-3 bond. From the perspective of chiral induction, photoisomerization of cis-2,3-diphenyl-1-benzoylcyclopropane derivatives with chiral auxiliaries placed at the meta and para positions of the benzoyl group have been examined both in isotropic solution and within zeolites. Whereas in isotropic solution the chiral auxiliaries placed at the meta position exhibit very little influence during the conversion of triplet cis-2,3-diphenyl-1-benzoylcyclopropane derivatives, they have significant influence within zeolites. For example, a-methyl benzylamine placed at the meta position of the benzoyl group (via an amide bond) yields the trans isomer with a diastereoselectivity (de) of 71% within NaY zeolite, whereas in solution no de is obtained. The chiral induction process within zeolites depends on the nature of the alkali ion and on the presence of water. Results suggest that the chiral auxiliary is able to control the bond being cleaved (C-1-C-2 VS. C-1-C-3 bond) within a zeolite, but it is unable to do so in an isotropic solution.
URI: http://dx.doi.org/10.1021/jo049697n
http://dspace.library.iitb.ac.in/xmlui/handle/10054/3822
http://hdl.handle.net/10054/3822
ISSN: 0022-3263
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