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. 2014 Jul 23;136(29):10270-3.
doi: 10.1021/ja506170g. Epub 2014 Jul 9.

Synthesis of (-)-pseudotabersonine, (-)-pseudovincadifformine, and (+)-coronaridine enabled by photoredox catalysis in flow

Joel W Beatty  1 , Corey R J Stephenson
Affiliations

Synthesis of (-)-pseudotabersonine, (-)-pseudovincadifformine, and (+)-coronaridine enabled by photoredox catalysis in flow

Joel W Beatty et al. J Am Chem Soc. .

Abstract

Natural product modification with photoredox catalysis allows for mild, chemoselective access to a wide array of related structures in complex areas of chemical space, providing the possibility for novel structural motifs as well as useful quantities of less abundant congeners. While amine additives have been used extensively as stoichiometric electron donors for photocatalysis, the controlled modification of amine substrates through single-electron oxidation is ideal for the synthesis and modification of alkaloids. Here, we report the conversion of the amine (+)-catharanthine into the natural products (-)-pseudotabersonine, (-)-pseudovincadifformine, and (+)-coronaridine utilizing visible light photoredox catalysis.

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Figures

Scheme 1
Scheme 1. Catharanthine Fragmentation Provides Access to Structurally Diverse Alkaloids
Scheme 2
Scheme 2. Synthesis of (−)-Pseudotabersonine
Scheme 3
Scheme 3. Synthesis of (+)-Coronaridine
Scheme 4
Scheme 4. Synthesis of (−)-Pseudovincadifformine
Scheme 5
Scheme 5. Proposed Catalytic Cycle for Fragmentation
Scheme 6
Scheme 6. Photocatalytic Fragmentation of Hydrogenated Iboga Alkaloids
Scheme 7
Scheme 7. Homodesmotic Strain Release Values
Scheme 8
Scheme 8. Synthetic summary
See this image and copyright information in PMC

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