Premium
Diastereoselective Preparation of Silylated Pyrrolidones through Palladium‐Catalysed Cyclisations
Author(s) -
Thorimbert Serge,
Giambastiani Giuliano,
Commandeur Claude,
Vitale Maxime,
Poli Giovanni,
Malacria Max
Publication year - 2003
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.200300086
Subject(s) - chemistry , palladium , moiety , stereoselectivity , allylic rearrangement , nitrogen atom , acetamide , carbon atom , medicinal chemistry , silicon , tsuji–trost reaction , ring (chemistry) , stereochemistry , organic chemistry , catalysis
A new palladium‐catalysed allylic alkylation affording silylated 3‐vinylpyrrolidones has been developed. The method relies upon the interaction between a stabilized acetamide enolate anion and a silicon‐containing, nitrogen‐tethered η 3 ‐allylpalladium moiety. Two variants have been studied, involving the location of the silicon atom on either olefinic carbon atom of the cyclisation precursor. In both cases 5‐ exo ring closure was the only cyclisation process observed. The stereoselectivity of these processes is discussed. These results contrast with related β‐oxo ester cyclisations, in which competitive 7‐ endo mode is observed. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)