Stereoselective Silylcupration of Conjugated Alkynes in Water at Room Temperature

Micellar catalysis enables copper‐catalyzed silylcupration of a variety of electron‐deficient alkynes, thereby providing access to isomerically pure E‐ or Z‐β‐silyl‐substituted carbonyl derivatives. These reactions take place in minutes, afford high yields and stereoselectivity, and are especially t...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2014-04, Vol.53 (16), p.4159-4163
Main Authors: Linstadt, Roscoe T. H., Peterson, Carl A., Lippincott, Daniel J., Jette, Carina I., Lipshutz, Bruce H.
Format: Article
Language:English
Subjects:
Alkynes
Carbonyls
Catalysis
Compatibility
copper
Derivatives
Environmental impact
green chemistry
Low level
micellar catalysis
organosilicon compounds
Recycled
Recycling
silylboronates
Temperature
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Summary:Micellar catalysis enables copper‐catalyzed silylcupration of a variety of electron‐deficient alkynes, thereby providing access to isomerically pure E‐ or Z‐β‐silyl‐substituted carbonyl derivatives. These reactions take place in minutes, afford high yields and stereoselectivity, and are especially tolerant of functional groups present in the substrates. The aqueous reaction medium has been successfully recycled several times, and a substrate/catalyst ratio of 10,000:1 has been documented for this methodology. Fast, cheap, and green: Micellar catalysis enables the selective construction of a variety β‐silyl‐substituted carbonyl derivatives under mild aqueous conditions. The reaction is catalyzed by low levels of CuI, is compatible with numerous electron‐withdrawing groups, affords high yields, and provides opportunities for scale‐up and recycling of the reaction medium. The environmental impact, as measured by E Factors, is very low.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.201311035