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, V. Ramamurthy

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11 Scopus citations

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

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ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

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