Efficient Allylation of Nucleophiles Catalyzed by a Bifunctional Heterogeneous Palladium Complex‐Tertiary Amine System. Issue 5 (19th March 2013)

• Record Type: Journal Article
• Authors: Noda, Hiroto; Motokura, Ken; Miyaji, Akimitsu; Baba, Toshihide
• Is Part Of: Advanced synthesis & catalysis. Volume 355:Issue 5(2013)
• Page Start: 973
• Page End: 980
• Publication Date: 2013-03-19
• Subjects: Catalysis -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Chemistry -- Periodicals; Chemistry, Technical -- Periodicals; Chemistry -- Periodicals; Catalysis -- Periodicals; Technology, Pharmaceutical -- Periodicals; 547.2
• DOI: 10.1002/adsc.201300063
• Languages: English
• ISSNs: 1615-4150

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>We demonstrate the synergistic catalysis of a silica‐supported diaminopalladium complex and a tertiary amine (SiO₂/diamine/Pd/NEt₂) 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 SiO₂/diamine/Pd/NEt₂ 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 &gt;99% yield at 70 °C for 5 h. The yield of allylated products was 26% for SiO₂/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 SiO₂/diamine/Pd/NEt₂, 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 <italic>para</italic> position resulted in high product yields. The SiO₂/diamine/Pd/NEt₂ catalyst was reusable at least 4 times without appreciable loss of its activity and selectivity in the reaction of <italic>p</italic>‐chlorophenol.</p> </abstract>