ISSN:
0947-3440
Schlagwort(e):
Rhodium complexes, chiral
;
Hydrogenation
;
Diolefins
;
Selectivity
;
Chemistry
;
Organic Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
Kinetic Investigations of the Hydrogenation of Ligands in Catalyst Precursors for Asymmetric Reduction of Prochiral OlefinesHerrn Professor Kurt Madeja zum 70. Geburtstag gewidmet.The comparison of chiral rhodium(I) complex catalysts of the type [Rh(L)PP*]A (L = cyclic diolefin; PP* = chiral bis(phosphane) and A = anion like BF4-) regarding their hydrogenating activity against prochiral substrates is hampered by the induction period in the hydrogen consumption which can be attributed to the formation of the catalytically active species from the diolefin precatalyst. The competing hydrogenation of diolefin [e.g. cis,cis-cycloocta-1,5-diene (COD), norborna-2,5-diene (NBD)] and prochiral substrate may cause a maximum of the hydrogenation rate, which is characteristic for different catalyst/substrate/solvent systems. Michaelis-Menten rate constants for the hydrogenation of COD and NBD were determined for different chiral catalysts by stoichiometric and catalytic hydrogenations. The rate constants differ for one selected diolefin up to a factor of 40. The hydrogenation of NBD is generally 5-8 times faster than the COD hydrogenation. In the special case of precatalysts based on he-xopyranoside bis(phosphinites) the rate constants for the NBD hydrogenation in comparison with those for COD are higher up to a factor of 48. In some cases the hydrogenation of the mono-ene is faster than that of the diolefin (e.g. COD, NBD). The high hydrogenation rate reported in the literature for some precatalysts in the asymmetric hydrogenation of prochiral olefins is caused in part by the relatively fast diolefin hydrogenation which facilitates the complete formation of the catalyst. The influence of substrate, solvent, and some experimental conditions on the induction period will be discussed.
Zusätzliches Material:
7 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/jlac.199519950378
