Azide/oxygen photocatalysis with homogeneous and heterogeneous photocatalysts for 1,2-aminohydroxylation of acyclic/cyclic alkenes and Michael acceptors

Azide/oxygen photocatalysis with homogeneous and heterogeneous photocatalysts for... Homogeneous as well as heterogeneous photocatalysts that are able to oxidize the azide anion with low competitive singlet oxygen quantum yields are used to generate azidyl radicals. These radicals add to electron-rich as well as electron-poor (Michael acceptors) alkenes, and carbon radicals are formed regioselectively. Trapping with triplet oxygen (type I photooxygenation) is diffusion controlled, and the initially formed peroxy radicals are reduced with regeneration of the photocatalyst. Fluorescence quenching studies reveal rapid photoinduced electron transfer in the first catalysis step. The lack of rearrangement products in the bicyclic terpene series (pinenes, limonene) accounts for rapid subsequent oxygen trapping and back electron transfer steps. The 1,2-azidohydroperoxidation enables synthesis of 1,2-azidoalcohols and 1,2-aminoalcohols by different reduction protocols. Substrate modification and combination of type II photooxygenation with electron transfer photocatalysis allows the synthesis of 1-amino-2,3-diols and 2-amino-1,3-diols. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Research on Chemical Intermediates Springer Journals

Azide/oxygen photocatalysis with homogeneous and heterogeneous photocatalysts for 1,2-aminohydroxylation of acyclic/cyclic alkenes and Michael acceptors

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Publisher
Springer Netherlands
Copyright
Copyright © 2012 by Springer Science+Business Media B.V.
Subject
Chemistry; Catalysis; Physical Chemistry; Inorganic Chemistry
ISSN
0922-6168
eISSN
1568-5675
D.O.I.
10.1007/s11164-012-0629-3
Publisher site
See Article on Publisher Site

Abstract

Homogeneous as well as heterogeneous photocatalysts that are able to oxidize the azide anion with low competitive singlet oxygen quantum yields are used to generate azidyl radicals. These radicals add to electron-rich as well as electron-poor (Michael acceptors) alkenes, and carbon radicals are formed regioselectively. Trapping with triplet oxygen (type I photooxygenation) is diffusion controlled, and the initially formed peroxy radicals are reduced with regeneration of the photocatalyst. Fluorescence quenching studies reveal rapid photoinduced electron transfer in the first catalysis step. The lack of rearrangement products in the bicyclic terpene series (pinenes, limonene) accounts for rapid subsequent oxygen trapping and back electron transfer steps. The 1,2-azidohydroperoxidation enables synthesis of 1,2-azidoalcohols and 1,2-aminoalcohols by different reduction protocols. Substrate modification and combination of type II photooxygenation with electron transfer photocatalysis allows the synthesis of 1-amino-2,3-diols and 2-amino-1,3-diols.

Journal

Research on Chemical IntermediatesSpringer Journals

Published: Jun 12, 2012

References

  • Green oxidation with aqueous hydrogen peroxide
    Noyori, R; Aoki, M; Sato, K
  • On inventing reactions for atom economy
    Trost, BM
  • Azidohydroperoxidation of pinenes: stereoselectivity pattern and the first X-ray structure of a 2-azidohydroperoxide
    Griesbeck, AG; Lex, J; Saygin, KM; Steinwascher, J
  • Quantum yield of singlet oxygen production by xanthene derivatives
    Gandin, E; Lion, Y; Vorst, A
  • Organic azides: an exploding diversity of a unique class of compounds
    Bräse, S; Gil, C; Knepper, K; Zimmermann, V

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