Pyranophane Transannular Diels−Alder Approach to (+)-Chatancin: A Biomimetic Asymmetric Total Synthesis
An asymmetric total synthesis of (+)-chatancin was achieved via a transannular Diels−Alder (TADA) reaction of an in situ generated macrocyclic pyranophane pseudobase. The presented route constitutes the second of two proposed biosynthetic pathways that involves a TADA reaction. It links this diterpe...
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Veröffentlicht in: | Journal of organic chemistry 2003-12, Vol.68 (26), p.9983-9987 |
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Format: | Artikel |
Sprache: | eng |
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Zusammenfassung: | An asymmetric total synthesis of (+)-chatancin was achieved via a transannular Diels−Alder (TADA) reaction of an in situ generated macrocyclic pyranophane pseudobase. The presented route constitutes the second of two proposed biosynthetic pathways that involves a TADA reaction. It links this diterpene biogenetically to the cembranoids. A set of TADA selection rules that rationalize the formation of (+)-chatancin from a dynamic equilibrium of four 2-hydroxy-2H-pyrane bicycles and their 16 potential TADA transition states are also outlined. Beyond the TADA reaction, highlights of the synthetic work include the assembly of a chiral acyclic macrocyclization substrate from (S)-citronellol and an efficient macrocyclization via a β-ketosulfoxyde/enone Michael addition. |
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ISSN: | 0022-3263 1520-6904 |
DOI: | 10.1021/jo035193y |