Preparation of 2-trialkylsiloxy-substituted 1,3-dienes and their Diels-Alder/cross-coupling reactions
ABSTRACT [reaction: see text] 2-Triethylsiloxy-substituted 1,3-butadiene has been prepared in gram quantities from chloroprene via a simple synthetic procedure. Silatrane and catechol-substituted analogues of this main group element substituted diene were prepared by ligand exchange and characterized by X-ray crystallography in addition to standard spectroscopic techniques. Diels-Alder reactions of these dienes are reported as well as subsequent TBAF assisted/Pd-catalyzed Hiyama cross-coupling reactions of those Diels-Alder adducts.
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ABSTRACT: The palladium-catalyzed silylation of aryl chlorides with silylsilatranes proceeds under activator-free conditions; hence, wide functional group compatibility is displayed and boryl and siloxy groups are able to survive. Experimental and computational studies revealed that smooth transmetalation from the silylsilatrane to the arylpalladium chloride is facilitated by strong interaction between the Lewis acidic silicon and the chloride.Chemistry - An Asian Journal 08/2014; 10(1). DOI:10.1002/asia.201402595 · 4.57 Impact Factor