Premium
Efficient Synthesis of 4‐(3′‐Furanyl)butenolide Derivatives via Pd II ‐Catalyzed Oxidative Heterodimeric Cyclization Reaction of 2,3‐Allenoic Acids and 1,2‐Allenyl Ketones
Author(s) -
Ma Shengming,
Yu Zhanqian
Publication year - 2004
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.200305341
Subject(s) - chemistry , butenolide , catalysis , cinchonidine , optically active , benzylamine , oxidative phosphorylation , medicinal chemistry , enantioselective synthesis , oxidative addition , combinatorial chemistry , stereochemistry , organic chemistry , biochemistry
The oxidative cyclization/dimerization reaction between two classes of allenes with different functionalities was reported to provide an efficient route to polysubstituted 4‐(3′‐furanyl)‐2(5 H )‐furanones, which are not readily available from the known methods. The highly optically active butenolides could be easily formed from the optically active 2,3‐allenoic acids, which was obtained conveniently through chiral resolution with optically active amines, that is, cinchonidine or α‐methyl benzylamine. A mechanistic study showed that the reaction proceeded via a matched double oxypalladation–reductive elimination process. The Pd II species may be regenerated via the subsequent cyclometallation of two equivalents of 1,2‐allenyl ketones with Pd 0 and protonlysis of Pd enolates formed with the in situ generated HCl.