Palladium-Catalyzed Fluoride-Free Cross-Coupling of Intramolecularly Activated Alkenylsilanes and Alkenylgermanes: Synthesis of Tamoxifen as a Synthetic Application

We have demonstrated that intramolecular hypercoordination of a carboxylic acid is a powerful activation strategy for the palladium‐catalyzed cross‐coupling reaction of trialkyl(vinyl)silanes and trialkyl(vinyl)germanes under fluoride‐free conditions. Z‐β‐Trialkylsilyl‐ and Z‐β‐trialkylgermylacrylic...

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Bibliographic Details
Published in:Advanced synthesis & catalysis 2012-03, Vol.354 (4), p.642-650
Main Authors: Matsumoto, Kenji, Shindo, Mitsuru
Format: Article
Language:English
Subjects:
Catalysis
Chemistry
cross-coupling
Exact sciences and technology
General and physical chemistry
germanium
hypervalent compounds
olefination
Organic chemistry
Organometalloidal and organometallic compounds
Preparations and properties
Si derivatives
silicon
tamoxifen
Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
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Summary:We have demonstrated that intramolecular hypercoordination of a carboxylic acid is a powerful activation strategy for the palladium‐catalyzed cross‐coupling reaction of trialkyl(vinyl)silanes and trialkyl(vinyl)germanes under fluoride‐free conditions. Z‐β‐Trialkylsilyl‐ and Z‐β‐trialkylgermylacrylic acids, synthesized stereoselectively by olefination with ynolates, are highly stable and useful reagents for cross‐coupling with a variety of aryl iodides to provide tetrasubstituted olefins possessing different carbon substituents in a stereocontrolled and diversity‐oriented manner. An application to a stereoselective synthesis of (Z)‐tamoxifen is also reported.
ISSN:1615-4150
1615-4169
DOI:10.1002/adsc.201100627