Premium
Oxidation of Terminal Olefins by Dioxygen in the Presence of Pd II (NH 3 ) x ‐Cu II ‐Li I ‐Cl − or Pd II (or Pd 0 )/Zeolites/Cu II ‐Li I ‐Cl − Systems and a Coreducer (Ethanol)
Author(s) -
Mohammedi Ourida,
Chemat Farid,
Brégeault JeanMarie
Publication year - 1998
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/(sici)1099-0690(199809)1998:9<1901::aid-ejoc1901>3.0.co;2-r
Subject(s) - chemistry , isomerization , catalysis , faujasite , zeolite , mordenite , acetaldehyde , selectivity , cyclohexene , solvent , anhydrous , medicinal chemistry , ammonia , organic chemistry , photochemistry , ethanol
Simple ammonia complexes { cis ‐[PdCl 2 (NH 3 ) 2 ], [Pd(NH 3 ) 4 ]Cl 2 or [Pd(NO 2 ) 2 (NH 3 ) 2 ]} with copper(II) chloride and LiCl or Pd II (or Pd 0 ) inserted into zeolite (faujasite Y or mordenite Z)/Cu II ‐Li I ‐Cl − precursors in anhydrous ethanol catalyse the oxidation of terminal olefins to methyl ketones by dioxygen. One oxygen atom is incorporated into the olefinic substrate, while the other is involved in a cooxidation process of the solvent leading to the formation of water. With 1‐octene and ethanol, octan‐2‐one can be obtained selectively (up to 99 %), acetaldehyde and diethyl acetal being the main cooxidation products. Chorohydridopalladium species are key intermediates in the isomerization of 1‐alkenes; it appears that the introduction of NH 3 , NO 2 − or zeolite ligands reduces the extent of isomerization and subsequently the formation of isomeric ketones (octan‐3‐one and octan‐4‐one). Although homogeneous catalysis cannot be ruled out, the improved selectivities and variations of selectivity and conversion with different zeolites suggest that a “ship‐in‐a‐bottle” catalysis may be important.