Irreversible catalytic ester hydrolysis of allyl esters to give acids and aldehydes by homogeneous ruthenium and ruthenium/palladium dual catalyst systems

Asami Nakamura, Akiyuki Hamasaki, Sachihiko Goto, Masaru Utsunomiya, Makoto Tokunaga

Research output: Contribution to journalArticle

10 Citations (Scopus)

Abstract

An irreversible hydrolysis reaction of allyl esters (1) into carboxylic acids (2) and propanal (3) was achieved with a ruthenium/palladium (Ru/Pd) dual catalyst system. The optimized catalysts consists of a 1:1:1 mixture of (cyclopentadienyl)tris(acetonitrile)ruthenium hexafluorophosphate {[RuCp(MeCN)3] PF6}, bis(acetonitrile)palladium dichloride [PdCl2(MeCN)2] and 1,6-bis(diphenylphosphanyl)hexane (DPPHex). The reaction proceeds via isomerization of allyl esters to 1-propenyl esters and hydrolysis of them to give 2 and 3. The first isomerization step was virtually catalyzed by the Ru components and the second hydrolysis step was mainly catalyzed by the Pd components. The optimized bidentate phosphine (DPPHex) which has long alkylene chain effectively generates two vacant sites on the Ru centers by bridging coordination. When a chelating bidentate phosphine such as DPPE was employed, only one vacant site remained on the Ru center and resulted in a low activity. This chelating Ru complex of DPPE formed even in the presence of 2 equivalents of Ru or additional 1 equivalent of Pd. These differences in coordination behaviour between DPPHex and 1,2- bis(diphenylphosphanyl)ethane (DPPE) cause the differences of the catalytic activity in the first step. The phosphine coordination to Pd center slightly decreases the activity of second hydrolysis step but which was compensated by the increasing of the stability of Pd. On the whole, the optimized Ru/Pd dual catalyst system exhibited good performances on the irreversible hydrolysis of allyl esters.

Original languageEnglish
Pages (from-to)973-984
Number of pages12
JournalAdvanced Synthesis and Catalysis
Volume353
Issue number6
DOIs
Publication statusPublished - Apr 18 2011

Fingerprint

phosphine
Ruthenium
Palladium
Aldehydes
Hydrolysis
Esters
Ethane
Hexanes
Catalysts
Hexane
Acids
Isomerization
Chelation
Acetonitrile
Carboxylic Acids
Carboxylic acids
Catalyst activity

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Organic Chemistry

Cite this

Irreversible catalytic ester hydrolysis of allyl esters to give acids and aldehydes by homogeneous ruthenium and ruthenium/palladium dual catalyst systems. / Nakamura, Asami; Hamasaki, Akiyuki; Goto, Sachihiko; Utsunomiya, Masaru; Tokunaga, Makoto.

In: Advanced Synthesis and Catalysis, Vol. 353, No. 6, 18.04.2011, p. 973-984.

Research output: Contribution to journalArticle

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