Premium
Efficient Allylation of Nucleophiles Catalyzed by a Bifunctional Heterogeneous Palladium Complex‐Tertiary Amine System
Author(s) -
Noda Hiroto,
Motokura Ken,
Miyaji Akimitsu,
Baba Toshihide
Publication year - 2013
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.201300063
Subject(s) - chemistry , diamine , catalysis , bifunctional , synergistic catalysis , nucleophile , palladium , yield (engineering) , amine gas treating , organic chemistry , tertiary amine , medicinal chemistry , phenols , materials science , metallurgy
We demonstrate the synergistic catalysis of a silica‐supported diaminopalladium complex and a tertiary amine (SiO 2 /diamine/Pd/NEt 2 ) as well as synthetic scope of the Tsuji–Trost reaction of 1,3‐dicarbonyls, phenols, and carboxylic acids with allyl carbonate and acetates. The synergistic catalysis of SiO 2 /diamine/Pd/NEt 2 exhibited wide applicability and high activity for the Tsuji–Trost reaction. For example, the reaction of ethyl 3‐oxobutanate with allyl methyl carbonate afforded the allylated product in >99% yield at 70 °C for 5 h. The yield of allylated products was 26% for SiO 2 /diamine/Pd, without immobilization of the tertiary amine group. In the reaction of 1.0 mmol of ethyl 3‐oxobutanate using 0.60 μmol of Pd in SiO 2 /diamine/Pd/NEt 2 , the turnover number (TON) of Pd reached up to 1070 within 24 h. Phenols with electron‐withdrawing groups, such as nitro and chloro groups, on the para position resulted in high product yields. The SiO 2 /diamine/Pd/NEt 2 catalyst was reusable at least 4 times without appreciable loss of its activity and selectivity in the reaction of p ‐chlorophenol.