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. 2014 Jun 3:10:1272-81.
doi: 10.3762/bjoc.10.128. eCollection 2014.

Cyclization-endoperoxidation cascade reactions of dienes mediated by a pyrylium photoredox catalyst

Nathan J Gesmundo  1 , David A Nicewicz  1
Affiliations

Cyclization-endoperoxidation cascade reactions of dienes mediated by a pyrylium photoredox catalyst

Nathan J Gesmundo et al. Beilstein J Org Chem. .

Abstract

Triarylpyrylium salts were employed as single electron photooxidants to catalyze a cyclization-endoperoxidation cascade of dienes. The transformation is presumed to proceed via the intermediacy of diene cation radicals. The nature of the diene component was investigated in this context to determine the structural requirements necessary for successful reactivity. Several unique endoperoxide structures were synthesized in yields up to 79%.

Keywords: alkene; cascade; endoperoxide; oxidation; photoredox catalysis.

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Figures

Figure 1
Figure 1
Selected examples of endoperoxide-containing natural products.
Scheme 1
Scheme 1
Endoperoxide formation via cation radicals. In both examples, single electron oxidation is followed quickly by cyclization to form stabilized distonic cation radical intermediates. The distonic intermediates are trapped by O2 and furnish the shown bicyclic products after reduction.
Scheme 2
Scheme 2
Diversification strategy for endoperoxide synthesis by single electron transfer. E*red vs SCE [20].
Figure 2
Figure 2
ORTEP of 3a.
Scheme 3
Scheme 3
Proposed mechanism for endoperoxide synthesis from tethered dienes.
Scheme 4
Scheme 4
Competing formal [3,3] pathway.
See this image and copyright information in PMC

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