Light-induced geometric isomerization of 1,2-diphenylcyclopropanes included within Y zeolites: Role of Cation-guest binding

Lakshmi S. Kaanumalle, J. Sivaguru, R. B. Sunoj, P. H. Lakshminarasimhan, J. Chandrasekhar, Vaidhyanathan Ramamurthy

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Abstract

Through a systematic study of several diphenylcyclopropane derivatives, we have inferred that the cations present within a zeolite control the excited-state chemistry of these systems. In the parent 1,2-diphenylcylopropane, the cation binds to the two phenyl rings in a sandwich-type arrangement, and such a mode of binding prevents cis-to-trans isomerization. Once an ester or amide group is introduced into the system (derivatives of 2β,3β-diphenylcyclopropane-1α-carboxylic acid), the cation binds to the carbonyl group present in these chromophores and such a binding has no influence on the cis-trans isomerization process. Cation-reactant structures computed at density functional theory level have been very valuable in rationalizing the observed photochemical behavior of diphenylcyclopropane derivatives included in zeolites. While the parent system, 1,2-diphenylcylopropane, has been extensively investigated in the context of chiral induction in solution, owing to its failure to isomerize from cis to trans, the same could not be investigated in zeolites. However, esters of 2β,3β-diphenylcyclopropane-1α-carboxylic acid could be studied within zeolites in the context of chiral induction. Chiral induction as high 20% ee and 55% de has been obtained with selected systems. These numbers, although low, are much higher than what has been obtained in solution with the same system or with the parent system by other investigators (maximum ∼10% ee).

Original languageEnglish
Pages (from-to)8711-8720
Number of pages10
JournalJournal of Organic Chemistry
Volume67
Issue number25
DOIs
StatePublished - Dec 13 2002
Externally publishedYes

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Zeolites
Isomerization
Cations
Carboxylic Acids
Derivatives
Esters
Chromophores
Excited states
Amides
Density functional theory
diphenylcyclopropane

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Light-induced geometric isomerization of 1,2-diphenylcyclopropanes included within Y zeolites : Role of Cation-guest binding. / Kaanumalle, Lakshmi S.; Sivaguru, J.; Sunoj, R. B.; Lakshminarasimhan, P. H.; Chandrasekhar, J.; Ramamurthy, Vaidhyanathan.

In: Journal of Organic Chemistry, Vol. 67, No. 25, 13.12.2002, p. 8711-8720.

Research output: Contribution to journalArticle

Kaanumalle, Lakshmi S. ; Sivaguru, J. ; Sunoj, R. B. ; Lakshminarasimhan, P. H. ; Chandrasekhar, J. ; Ramamurthy, Vaidhyanathan. / Light-induced geometric isomerization of 1,2-diphenylcyclopropanes included within Y zeolites : Role of Cation-guest binding. In: Journal of Organic Chemistry. 2002 ; Vol. 67, No. 25. pp. 8711-8720.
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abstract = "Through a systematic study of several diphenylcyclopropane derivatives, we have inferred that the cations present within a zeolite control the excited-state chemistry of these systems. In the parent 1,2-diphenylcylopropane, the cation binds to the two phenyl rings in a sandwich-type arrangement, and such a mode of binding prevents cis-to-trans isomerization. Once an ester or amide group is introduced into the system (derivatives of 2β,3β-diphenylcyclopropane-1α-carboxylic acid), the cation binds to the carbonyl group present in these chromophores and such a binding has no influence on the cis-trans isomerization process. Cation-reactant structures computed at density functional theory level have been very valuable in rationalizing the observed photochemical behavior of diphenylcyclopropane derivatives included in zeolites. While the parent system, 1,2-diphenylcylopropane, has been extensively investigated in the context of chiral induction in solution, owing to its failure to isomerize from cis to trans, the same could not be investigated in zeolites. However, esters of 2β,3β-diphenylcyclopropane-1α-carboxylic acid could be studied within zeolites in the context of chiral induction. Chiral induction as high 20{\%} ee and 55{\%} de has been obtained with selected systems. These numbers, although low, are much higher than what has been obtained in solution with the same system or with the parent system by other investigators (maximum ∼10{\%} ee).",
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