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Ruthenium‐Catalyzed O ‐Allylation of Phenols from Allylic Chlorides via Cationic [Cp*(η 3 ‐allyl)(MeCN)RuX][PF 6 ] Complexes
Author(s) -
Mbaye Mbaye D.,
Demerseman Bernard,
Renaud JeanLuc,
Toupet Loïc,
Bruneau Christian
Publication year - 2004
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.200404023
Subject(s) - allylic rearrangement , chemistry , regioselectivity , ruthenium , cationic polymerization , medicinal chemistry , ligand (biochemistry) , nucleophile , catalysis , aryl , organic chemistry , alkyl , biochemistry , receptor
The [Cp*(MeCN) 3 Ru(II)][PF 6 ] complex is an efficient catalyst precursor for the O ‐allylation of phenols with allylic chlorides in the presence of K 2 CO 3 under mild conditions. This ruthenium precursor affords branched allyl aryl ethers according to a regioselective reaction, which contrasts with the uncatalyzed nucleophilic substitution from the same substrates. Stable (η 3 ‐allyl)Ru(IV) cationic complexes resulting from the reaction of [Cp*(MeCN) 3 Ru][PF 6 ] with allylic halides were identified as intermediate catalytic species. An X‐ray structure determination of the complex [Cp*(MeCHCHCH 2 )(MeCN)RuBr][PF 6 ] disclosed an ( endo‐trans‐ MeCHCHCH 2 ) allylic ligand. The structural information obtained from the study of Cp*(allyl)Ru(IV) complexes indicated that electronic effects at the coordinated allylic ligand likely account for the better regioselectivity obtained from cinnamyl chloride as compared to aliphatic allylic chlorides.