Ciba-geigy Corporation

Solvias Ag

Novartis Ag

Heidi Landert

Felix Spindler

Benoit Pugin

Andreas Pfaltz

Amina Wirth-Tijani

Matthias Lotz

Benoît Pugin

Björn Gschwend

Adrian Wyss

Raphael Aardoom

Giorgio Pioda

Bjoern Gschwend

Compounds of the formula (I) in the form of a mixture of predominantly one diastereomer or in the form of pure diastereomers,Z-Q-P*RR&#x2003;&#x2003;(I),wherein:

Bidentate chiral ligands for use in catalytic asymmetric addition reactions

Compounds of the formula (I), in the form of mixtures comprising predominantly one diastereomer or in the form of pure diastereomers, Z-Q-P*RR(I) in which Zis a C-bonded, secondary phosphine group &#x2014;P(R); in which R is in each case independently hydrocarbon radicals or heterohydrocarbon radicals, or Zis the &#x2014;P*RRgroup; Q is a bivalent, achiral, aromatic base skeleton, a bivalent, achiral ferrocene base skeleton, an optionally substituted bivalent cycloalkane or heterocycloalkane skeleton, or a C-C-alkylene skeleton.

Compounds of the formula I, in the form of mixtures comprising predominantly one enantiomer or in the form of pure enantiomers, secondary phosphine-Q-P*(&#x2550;O)HR(I) in which secondary phosphine is a C-bonded, secondary phosphine group &#x2014;P(R); in which R is in each case independently hydrocarbon radicals or heterohydrocarbon radicals; Q is a bivalent, achiral, aromatic base skeleton, a bivalent, achiral ferrocene base skeleton, an optionally substituted bivalent cycloalkane or heterocycloalkane skeleton, or a C1-C4-alkylene skeleton, and in which base skeletons a secondary phosphine group is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C-C-alkylene group, and in which base skeletons a P-chiral group &#x2014;P*(O)HRis bonded to a carbon atom such that the phosphorus atoms are linked via 1 to 7 atoms of a carbon chain optionally interrupted by heteroatoms from the group of O, S, N, Fe or Si; P* is a chiral phosphorus atom; and Ris a hydrocarbon radical, a C-bonded heterohydrocarbon radical or a ferrocenyl radical, with the proviso that Ris an achiral ferrocenyl radical when Q is an achiral ferrocenyl base skeleton. Metal complexes of these ligands in a molar ratio of ligand to metal of about 1.3:1 to 0.9:1 are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.

Bidentate secondary phosphine oxide chiral ligands for use in asymmetric addition reactions

The invention relates to 1,2-ferrocenyldiphosphines which contain a functional group in the 1&prime; position either directly or via a bridging group, and also a process for their preparation. The compounds are important for transition metal complexes containing d-8 metals such as Rh, Ru, Pd or Ir. These transition metal complexes are widely used in the hydrogenation of organic double or triple bonds, in particular olefinic double bonds and carbon-heteroatom double bonds. The complexes are particularly suitable for enantioselective hydrogenation using chiral ferrocenyldiphosphines and corresponding prochiral unsaturated compounds. Ferrocenyldiphosphines having a functional group in the 1&prime; position are also important intermediates for ferrocenyldiphosphine ligands and their metal complexes of d-8 metals such as rhodium, ruthenium, palladium or iridium which are bound to inorganic polymeric supports via this functional group. These metal complexes bound to an inorganic or organic support material are likewise very suitable for the hydrogenation of organic double or triple bonds.

Functionalized ferrocenyldiphosphines, a process for their preparation and their use

Chiral ferrocenyls

Compounds of formula I ##STR1## wherein R.sub.1 is C.sub.1 -C.sub.8 alkyl, phenyl or phenyl which is substituted by 1 to 3 C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy groups; R.sub.2 and R.sub.3 are each independently of the other typically C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, phenyl, or C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, or phenyl which is substituted by one to three identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or halogen; R.sub.10 and R.sub.11 are identical and are typically C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl or phenyl which is substituted by 1 to 3 identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or halogen; or R.sub.10 and R.sub.11 are different and are C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, phenyl or phenyl which is substituted by 1 to 3 identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or halogen, and * denotes a stereogenic carbon atom, in the form of their racemates and diastereoisomers or mixtures of diastereoisomers. Rhodium and iridium complexes with these ligands are suitable for use as homogeneous enantioselective catalysts for the hydrogenation of prochiral compounds containing carbon double bonds or carbon/hetero atom double bonds.

Ferrocene diphosphines as ligands for homogeneous catalysts

Compounds of formula I ##STR1## wherein R.sub.1 is C.sub.1 -C.sub.8 alkyl, phenyl or phenyl which is substituted by 1 to 3 C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy groups; R.sub.2 and R.sub.3 are each independently of the other typically C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, phenyl, or C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, or phenyl which is substituted by one to three identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or halogen;

Compounds of the formula I ##STR1## wherein R.sub.1 is C.sub.1 -C.sub.8 alkyl, phenyl or phenyl which is substituted by 1 to 3 C.sub.1 -C.sub.4 alkyl or C.sub.1 -C.sub.4 alkoxy groups; R.sub.2 and R.sub.3 are each independently of the other typically C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, phenyl, or C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, or phenyl which is substituted by one to three identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or halogen; R.sub.10 and R.sub.11 are identical and are typically C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl or phenyl which is substituted by 1 to 3 identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or halogen; or R.sub.10 and R.sub.11 are different and are C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.12 cycloalkyl, C.sub.1 -C.sub.4 alkyl- or C.sub.1 -C.sub.4 alkoxy-substituted C.sub.5 -C.sub.12 cycloalkyl, phenyl or phenyl which is substituted by 1 to 3 identical or different members selected from the group consisting of C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy or halogen, and * denotes a stereogenic carbon atom, in the form of their racemates and diastereoisomers or mixtures of diastereoisomers.

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Bourrignon, Switzerland

Heidi Landert