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RESEARCH PRODUCT

PHOSPHORORGANISCHE VERBINDUNGEN 105.1Synthese chiraler und achiraler ditertiärer 1-Phosphino-2-Aminoethan-Derivate ([dbnd]P [sbnd]CH2[sbnd]CHR[sbnd]N[dbnd]) und einige Anwendungen

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Abstract Primary amines with an optical active ligand add to vinyl- and propenylphosphonium salts according the reaction schemes (5) and (6), forming compounds of the type E and F. F contains a new asymmetric center in the bridge giving rise to the formation of a mixture of diastereomers, which can be resolved. Phosphonium salts of type E and F with a benzyl group on the phosphonium center are cleaved reductively by alkali amalgams (Li/Hg; Na/Hg; K/Hg) forming tertiary phosphines with an aminogroup in the β-position. The reductive cleavage with alkali amalgams is superior to the cathodic cleavage. Application: The synthesis of Ni(O)- and Pd(O)-complexes of type J fails. Bis-phosphine complexes of type 21 are formed. The rate of the homogeneous hydrogenation of 1-hexene with Rh(I)-complexes (containing G as a ligand) has an optimum with respect to a Rh/Co-catalyst proportion of 1:2 to 1 : 1.6. The optical induction of the homogeneous hydrogenation of Z-N-Acylamino-cinnamic acid is lower than 5%. Vinyl- und...