Asymmetric induction during electron transfer mediated photoreduction of carbonyl compounds: Role of zeolites

J. Shailaja, Lakshmi S. Kaanumalle, Karthikeyan Sivasubramanian, Arunkumar Natarajan, Keith J. Ponchot, Ajit Pradhan, Vaidhyanathan Ramamurthy

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Photochemistry of 17 aryl alkyl ketones included within cation exchanged zeolites has been examined. In solution five of the 17 ketones undergo intramolecular hydrogen abstraction reaction even in the presence of a chiral amine and the rest are photoreduced to the corresponding alcohol. Within zeolites all 17 ketones yielded in presence of a chiral amine, the corresponding alcohol as the major product. When a chiral amine was used as the coadsorbent within alkali ion exchanged zeolites, enantiomerically enriched alcohol was formed in all cases. The best chiral induction was obtained with phenyl cyclohexyl ketone (enantiomeric excess: 68%). 1H-13C Cross Polarization Magic Angle Spinning (CP-MAS) experiments, with a model ketone (perdeuterated acetophenone) and chiral amine (pseudoephedrine) included within MY zeolites, suggested that the cation brings the reactant and the chiral amine closer. The role of the cation in such a process is also revealed by the computation results. The results presented here highlight the importance of a supramolecular structure in forcing a closer interaction between a reactant and a chiral inductor that could be used to achieve asymmetric induction in photoproducts.

Original languageEnglish
Pages (from-to)1561-1571
Number of pages11
JournalOrganic and Biomolecular Chemistry
Volume4
Issue number8
DOIs
StatePublished - Jun 5 2006

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Zeolites
Carbonyl compounds
carbonyl compounds
Ketones
ketones
zeolites
photochemical reactions
Amines
induction
amines
electron transfer
Electrons
Cations
alcohols
Alcohols
cations
Pseudoephedrine
Photochemistry
Magic angle spinning
Photochemical reactions

ASJC Scopus subject areas

  • Biochemistry, Genetics and Molecular Biology(all)
  • Chemistry(all)

Cite this

Asymmetric induction during electron transfer mediated photoreduction of carbonyl compounds : Role of zeolites. / Shailaja, J.; Kaanumalle, Lakshmi S.; Sivasubramanian, Karthikeyan; Natarajan, Arunkumar; Ponchot, Keith J.; Pradhan, Ajit; Ramamurthy, Vaidhyanathan.

In: Organic and Biomolecular Chemistry, Vol. 4, No. 8, 05.06.2006, p. 1561-1571.

Research output: Contribution to journalArticle

Shailaja, J, Kaanumalle, LS, Sivasubramanian, K, Natarajan, A, Ponchot, KJ, Pradhan, A & Ramamurthy, V 2006, 'Asymmetric induction during electron transfer mediated photoreduction of carbonyl compounds: Role of zeolites', Organic and Biomolecular Chemistry, vol. 4, no. 8, pp. 1561-1571. https://doi.org/10.1039/b517069a
Shailaja J, Kaanumalle LS, Sivasubramanian K, Natarajan A, Ponchot KJ, Pradhan A et al. Asymmetric induction during electron transfer mediated photoreduction of carbonyl compounds: Role of zeolites. Organic and Biomolecular Chemistry. 2006 Jun 5;4(8):1561-1571. https://doi.org/10.1039/b517069a
Shailaja, J. ; Kaanumalle, Lakshmi S. ; Sivasubramanian, Karthikeyan ; Natarajan, Arunkumar ; Ponchot, Keith J. ; Pradhan, Ajit ; Ramamurthy, Vaidhyanathan. / Asymmetric induction during electron transfer mediated photoreduction of carbonyl compounds : Role of zeolites. In: Organic and Biomolecular Chemistry. 2006 ; Vol. 4, No. 8. pp. 1561-1571.
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