Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 54, Issue 13, Pages 3978-3982Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201411618
Keywords
alkyne metathesis; hydrogenation; natural products; ruthenium; total synthesis
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Funding
- Austrian Science Fund (Erwin Schrodinger fellowship) [J3466 N28]
- MPG
- Austrian Science Fund (FWF) [J 3466] Funding Source: researchfish
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The important biochemical probe molecule brefeldin A (1) has served as an inspirational target in the past, but none of the many routes has actually delivered more than just a few milligrams of product, where documented. The approach described herein is clearly more efficient; it hinges upon the first implementation of ruthenium-catalyzed trans-hydrogenation in natural products total synthesis. Because this unorthodox reaction is selective for the triple bond and does not touch the transannular alkene or the lactone site of the cycloalkyne, it outperforms the classical Birch-type reduction that could not be applied at such a late stage. Other key steps en route to 1 comprise an iron-catalyzed reductive formation of a non-terminal alkyne, an asymmetric propiolate carbonyl addition mediated by a bulky amino alcohol, and amacrocyclization by ring-closing alkyne metathesis catalyzed by a molybdenum alkylidyne.
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