Highly Regioselective, Sequential, and Multiple Palladium-Catalyzed Arylations of Vinyl Ethers Carrying a Coordinating Auxiliary: An Example of a Heck Triarylation Process
- 1 August 2001
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 123 (34) , 8217-8225
- https://doi.org/10.1021/ja011019k
Abstract
This article describes the development of new auxiliary-accelerated Heck multiarylations by intramolecular presentation of the oxidative addition complex. The introduction of a specific, palladium-coordinating dimethylamino group allows for the desired chelation-accelerated and chelation-controlled tri- and diarylation reactions. We report (a) the first example of a Heck triarylation process, (b) highly selective palladium-catalyzed diarylations of alkyl vinyl ethers, and (c) a very rapid two-phase protocol for the microwave-assisted hydrolysis of amino-substituted, arylated vinyl ethers constituting an entry to diarylated ethanals and substituted desoxybenzoins. X-ray structures and product patterns support the suggested substrate-controlled Heck reaction pathway. The catalyst-directing alkyl dimethylamino functionality was rapidly (1−2 min) and efficiently released by microwave hydrolysis after Heck multiarylation reactions. The liberated aromatic carbonyl compounds were thereafter isolated and fully characterized.Keywords
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