Electroreductive Cleavage of Propargylic Acetates Through Polarity Inversion of in situ Generated Allenyl Palladium(II) Complexes and, in Part, Unusual Chemical Reduction Induced by Phosphine Ligand

Hideo Tanaka, Hiroaki Takeuchi, Qinghua Ren, Sigeru Torii

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

The electroreduction of propargyl acetates in the presence of a catalytic amount of PdCl2(PPh3)2/PPh3 in DMF containing Et4NOTs at ambient temperature under a constant current density (10 mA/cm2) afforded the corresponding allenes in 43-84% yields. The time-course of the reaction was monitored by HPLC, indicating that the allenes were formed immediately after the current was applied and that most of the starting materials were consumed when less than the theoretical amount of electricity (2 F/mol), typically 1.2-1.7 F/mol, was reached. Interestingly a considerable amount of phosphine oxide was formed in the electroreduction media. Neither the reductive cleavage of the propargylic acetates nor the formation of phosphine oxide occurred without electricity being applied. The unusual results suggest that chemical reduction with the phosphine ligand would take place, in part, during the course of the electroreduction. A plausible reaction mechanism is proposed involving electroreductive polarity inversion of in situ generated allenyl PdII-complex as well as chemical reduction with the triphenylphosphine ligand leading to allenyl anion species.

Original languageEnglish
Pages (from-to)769-772
Number of pages4
JournalElectroanalysis
Volume8
Issue number8-9
DOIs
Publication statusPublished - Jan 1 1996

Keywords

  • Allene
  • Palladium
  • Propargyl acetate
  • Reduction mechanism

ASJC Scopus subject areas

  • Analytical Chemistry
  • Electrochemistry

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