3173-79-3Relevant articles and documents
Turro et al.
, p. 2774,2775 (1965)
Phosphine-catalyzed stereoselective dimerizations of ketenes
Ibrahim, Ahmad A.,Wei, Pei-Hsun,Harzmann, Gero D.,Nalla, Divya,Mondal, Mukulesh,Wheeler, Kraig A.,Kerrigan, Nessan J.
, (2020/12/21)
Full details of optimisation studies of the phosphine-catalyzed ketene homodimerization reaction and the detailed development of an asymmetric variant are discussed. Studies towards the development of a phosphine-catalyzed ketene heterodimerization reaction are revealed. A discussion of possible reaction mechanisms for the dimerization reactions, supported by spectroscopic analysis of intermediates and trapping experiments, is also presented.
Mechanistic studies of the phosphine-catalyzed homodimerization of ketoketenes
Wei, Pei-Hsun,Ibrahim, Ahmad A.,Mondal, Mukulesh,Nalla, Divya,Harzmann, Gero D.,Tedeschi, Frank A.,Wheeler, Kraig A.,Kerrigan, Nessan J.
supporting information; experimental part, p. 6690 - 6694 (2011/02/24)
The mechanism of PBu3-catalyzed homodimerization of ketoketenes has been explored and compared with that of the previously reported trialkylphosphite-mediated reactions. NMR studies of the PBu3- catalyzed reaction implicated the involvement of tetravalent phosphonium intermediates. Phosphonium intermediates in the catalytic cycle were trapped through reaction with trimethylsilyl chloride and 4-chlorobenzaldehyde, and the resulting products were characterized. A method for the stoichiometric generation of phosphonium enolates was developed as a result of these studies. No evidence was obtained for the involvement of pentacovalent phosphorane intermediates in trialkylphosphine-catalyzed ketoketene homodimerization reactions, in contrast with the mechanism of the trialkylphosphite-mediated homodimerization of dimethylketene. An X-ray crystal structure analysis of methylphenylketene dimer showed that it possesses Z-geometry about the exocyclic olefin.
Ketene. Part 26. The Reactions of 3,4-Dihydroisoquinoline N-Oxide with Ketenes, and an Attempted Synthesis of 3,4-Dihydro-3,3-dimethylquinoline N-Oxide
Evans, Andrew R.,Martin, Russell,Taylor, Giles A.,Yap, C. H. Maurice
, p. 1635 - 1640 (2007/10/02)
3,4-Dihydroisoquinoline N-Oxide reacts with dimethylketene to form a 1:2 adduct (8) in addition to compounds (6) and (7).With cyano-t-butylketene and ethoxycarbonyl-t-butylketene the adducts (9a) and (9b) are formed. 3,3-Dimethyl-1,2,3,4-tetrahydroquinoline (21a) has been synthesized, but attempts to convert this into the nitrone (20b) were unsuccessful.