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stereospecific isomerization allylic amines with the aid of chiral phosphorated ligands.
stereospecific isomerization allylic amines with the aid of chiral phosphorated ligands.
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机译:借助手性磷酸化配体的立体有规异构化烯丙基胺。
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摘要
A process for the stereospecific isomerisation of prochiral allylic systems represented by the formula wherein R1 and R2 each represents an alkyl or alkenyl from 1 to 12 carbon atoms or an aryl group, possibly substituted by a hydroxy group; R3 and R4 represent independently of one another hydrogen, alkyl or alkenyl group of C1 to C12 or an aryl group; R5 is hydrogen or an alkyl or cycloalkyl group of 1 to 8 carbon atoms; R6 is an alkyl or cycloalkyl group of 1 to 8 carbon atoms; or R5 and R6 are taken together with the nitrogen atom to form a ring of 6 atoms containing oxygen to obtain represented by formula enamines where the symbols R1-R6 have the meanings assigned above, or imines represented by the formula where R1-R4 and R6 symbols have the meanings assigned above and R 5 is hydrogen, using catalysts Rh, Ir or Ru having at least one chiral phosphine ligand, the process being characterized as the phosphine ligand a ligand represented by the formula wherein Ar is phenyl or tolyl, R2 and R3 represent hydrogen or a unit of the type ZB¿- being B¿ a group linking the polymer Z and the ligand, selected from -C (O) groups -, - (CH2) m- or -NH-C (O) - (CH2) mC (O) -, m being an integer from 1 to 4, and Z is a polymer or copolymer selected from silica, polystyrene, the polyamides, polystyrene graft copolymers and polioxieti leno type "Tentagel", the functionalised polystyrene of the Merrifield resin type, aminomethylated polystyrene, or [4- (hydroxymethyl) phenoxymethyl] polystyrene, being excluded R2 = R3 = H.
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