Reductive dechlorination of aryl chlorides catalyzed by palladium complexes containing basic, chelating phosphines

Yehoshua Ben-David, Michael Gozin, Moshe Portnoy, David Milstein

Research output: Contribution to journalArticle

58 Citations (Scopus)

Abstract

Aryl chlorides undergo efficient, homogeneously catalyzed reductive dechlorination to the corresponding arenes using Pd(dippp)2 as catalyst [dippp=1,3-bis(diisopropylphosphino) propane], which may be generated in situ from Pd(OAc)2 and two equivalents of dippp. Two reducing systems are described: (a) sodium hydroxide in methanol; (b) sodium formate in alcohol or DMF. Base-sensitive functional groups (CHO, CN) do not survive the conditions of system (a), but remain unaffected during dechlorination with sodium formate. Various functional groups are tolerated, and high yields are obtained. The reaction rate is retarded by electron-donating substituents, indicating a rate-determining oxidative addition step. Reaction of the model complex (dippp)Pd(Ph)Cl with sodium formate in the presence of dippp leads to the formation of Pd(dippp)2 and benzene. Dippp homologues are also effective ligands in the catalytic reaction, the reactivity order being dippp > dippb > dippe. Iso-Pr3P is only marginally effective. A mechanistic interpretation of these observations is given.

Original languageEnglish
Pages (from-to)173-180
Number of pages8
JournalJournal of Molecular Catalysis
Volume73
Issue number2
DOIs
Publication statusPublished - 1992

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Dechlorination
Chelation
Palladium
Sodium
Functional groups
Propane
Reaction rates
Benzene
Methanol
Alcohols
Ligands
Catalysts
Electrons

Cite this

Reductive dechlorination of aryl chlorides catalyzed by palladium complexes containing basic, chelating phosphines. / Ben-David, Yehoshua; Gozin, Michael; Portnoy, Moshe; Milstein, David.

In: Journal of Molecular Catalysis, Vol. 73, No. 2, 1992, p. 173-180.

Research output: Contribution to journalArticle

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