ISSN:
1573-1111
Keywords:
Metalloenzymes
;
catalysis
;
oxidation
;
nickel
;
alkene
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Abstract New nickel catalysts have been developed for the oxidation of alkenes to epoxides, alcohols, aldehydes and ketones. Mechanistic studies indicate that the oxidation reactions are very sensitive to the nature of the catalyst; only certain ligands including salen and the macrocycles cyclam and dioxocyclam render Ni(II) effective as a catalyst. A Ni(III) or Ni(IV)-oxo species has been postulated as the catalytically active oxidant which leads to oxygen atom transfer to alkenes in a stepwise process. Both iodosylbenzene and hypochlorite have been used as terminal oxidants; both systems give high yields of epoxidation of alkenes and varying amounts of C=C bond cleavage products. In order to reach an ultimate goal of hydrocarbon oxidation within a molecular recognition system, new molecular receptors for organic substrates have been investigated. The receptors are constructed from two subunits of cholic acid and display amphophilic character — a hydrophobic exterior and a hydrophilic interior. Conformational properties in the presence of polar guests in CDCl3 are described.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF01060717
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