Constructing Quaternary Stereogenic Centers Using Tertiary Organocuprates and Tertiary Radicals. Total Synthesis of trans-Clerodane Natural Products

Constructing Quaternary Stereogenic Centers Using Tertiary Organocuprates and Tertiary Radicals. Total Synthesis of trans-Clerodane Natural Products

A new concise construction of trans-clerodane diterpenoids is reported in which oxacyclic and trans-hydronaphthalene fragments are coupled, and the critical C9-quaternary carbon stereocenter formed stereoselectively, by 1,6-addition of a tertiary cuprate or a tertiary carbon radical to β-vinylbuteno...

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Veröffentlicht in:Journal of the American Chemical Society 2015-01, Vol.137 (2), p.660-663
Hauptverfasser: Müller, Daniel S, Untiedt, Nicholas L, Dieskau, André P, Lackner, Gregory L, Overman, Larry E
Format: Artikel
Sprache:eng
Schlagworte:
Biological Products - chemical synthesis
Biological Products - chemistry
Chemistry Techniques, Synthetic
Copper - chemistry
Diterpenes, Clerodane - chemical synthesis
Diterpenes, Clerodane - chemistry
Free Radicals - chemistry
Stereoisomerism
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Zusammenfassung:A new concise construction of trans-clerodane diterpenoids is reported in which oxacyclic and trans-hydronaphthalene fragments are coupled, and the critical C9-quaternary carbon stereocenter formed stereoselectively, by 1,6-addition of a tertiary cuprate or a tertiary carbon radical to β-vinylbutenolide. This strategy is specifically illustrated by total syntheses of (−)-solidagolactone (4), (−)-16-hydroxycleroda-3,13-dien-15,16-olide (5, PL3), and (−)-annonene (6).
ISSN:0002-7863
1520-5126
DOI:10.1021/ja512527s