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Allylsilanes as Carbon Nucleophiles in the Palladium‐Catalyzed 1,4‐Oxidation of Conjugated Dienes
Author(s) -
Castaño Ana M.,
Persson B. Anders,
Bäckvall JanE.
Publication year - 1997
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.19970030320
Subject(s) - palladium , chemistry , medicinal chemistry , intramolecular force , diene , nucleophile , benzoquinone , catalysis , stereoselectivity , double bond , bicyclic molecule , conjugated system , organic chemistry , natural rubber , polymer
Palladium‐catalyzed oxidation of cyclic 1,3‐dienes 3, 5, 9, 11 , and 13 , with an allylsilane group in the side chain, led to an intramolecular 1,4‐ syn ‐addition to the conjugated diene through a carbocyclization. Acyclic trienesilanes 7 also underwent analogous 1,4‐oxidations. The reaction was carried out in acetone‐acetic acid (2:1) with a slight excess of LiCl. p ‐Benzoquinone was employed as the oxidant and Li 2 PdCl 4 as the catalyst. The reaction proceeds through an intramolecular trans addition of the allylsilane to a (π‐diene)palladium complex to produce a bicyclic (π‐allyl)palladium intermediate. Subsequent trans attack by chloride at the π‐allyl intermediate gives the product. The intermediate (π‐allyl)palladium complex was isolated and fully characterized. It was unambiguously demonstrated that the allylsilane had attacked the coordinated double bond trans to palladium ( trans ‐carbopalladation). The use of CuCl 2 as the oxidant, instead of p ‐benzoquinone, gave a less stereoselective addition, but interestingly, with the opposite stereochemistry.