7505-96-6Relevant articles and documents
Asymmetric catalysis, 132 Metal-catalyzed enantioselective α-Ketol rearrangements
Brunner, Henri,Stoehr, Frank
, p. 2777 - 2786 (2007/10/03)
Promoted by catalytic amounts of transition-metal complexes, the tertiary α-hydroxy ketones 1, 3, 5/6 undergo α-ketol rearrangements to afford equilibrium mixtures of isomers with a reorganization of the carbon skeleton. The range of metal complexes catalyzing the isomerizations is large; the best results were obtained with the catalyst systems NiCl2/ TMEDA, Ni(acac)2, and Ni(acac)2/TMEDA (TMEDA = N,N,N',N'-tetramethyl-1,2-diaminoethane). The catalytic rearrangements were performed at 130 °C in the absence of solvent, with a Ni/ligand/substrate ratio of 1:2:100. The equilibrium composition of the model system 1/2 is 12.5:87:5. The conversion of the achiral substrates 1 and 3 into the chiral products 2 and 4 can be used for kinetic resolution. However, the reverse reactions 2 → 1 and 4 → 3 in the equilibrations narrow the window for asymmetric induction with enantioselective catalysts of the metal component/optically active ligand type. In system 1, the highest enantiomeric excess was achieved with the catalyst systems NiCl2/pybox [18.9% (S)-2] and Ni(acac)2/pybox [19.3% (R)-2] {pybox = 2,6-bis[(S)-4-isopropyl(oxazolin-2'-yl)]pyridine}. The α-ketol rearrangement of 3 with the Ni(acac)2/pybox catalyst resulted in a maximum enantiomeric excess of 37.1% (S)-4.
Titanocenes, the use thereof, and n-substituted fluoroanilines
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, (2008/06/13)
Titanocenes containing two 5-membered cyclodienyl gropus, for example cyclopentadienyl, and one or two 6-membered carbocyclic or 5- or 6-membered heterocyclic aromatic rings which are substituted by a fluorine atom in at least one of the two ortho-positions to the titanium-carbon bond and contain, as further substituents, a substituted amino radical, are suitable as photoinitiators for radiation-induced polymerization of ethylenically unsaturated compounds.
Novel nitrogen-containing titanocenes, and the use thereof
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, (2008/06/13)
Titanocenes of the formula I STR1 in which R1 are cyclopentadienyl? groups and R2 and R3 are aromatic radicals which are substituted in both ortho-positions by fluorine and, in addition, are substituted by a pyrrylalkyl group, amidoalkyl group or imidoalkyl group, are suitable as photoinitiators for the photopolymerization of ethylenically unsaturated compounds.