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Cover Picture: Eur. J. Org. Chem. 21/2002
Author(s) -
Liepins Vilnis,
Bäckvall JanE.
Publication year - 2002
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Reports
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/1099-0690(200211)2002:21<3498::aid-ejoc3498>3.0.co;2-3
Subject(s) - chemistry , regioselectivity , electrophile , silylation , allylic rearrangement , reagent , medicinal chemistry , organic chemistry , electrophilic addition , copper , catalysis
Silylcupration reactions of 1,3‐dienes with a cyanocuprate reagent PhMe 2 SiCuCNLi produce a (4‐silyl‐2‐alken‐1‐yl)copper complex, which was trapped by electrophiles. The use of allylic phosphates as electrophiles resulted in highly regioselective reactions with overall 1,4‐addition of the silyl and allyl moieties across the diene. Water (H 3 O + ) or acetyl chloride as the electrophile afforded a mixture of 1,2‐ and 1,4‐addition products, whereas carbon dioxide gave a highly regioselective 1,2‐addition. The intermediate (4‐silyl‐2‐alken‐1‐yl)copper complexes were characterized by NMR spectroscopy. The mechanism of the silylcupration reaction of 1,3‐dienes and subsequent electrophilic trapping is discussed. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)