Solvias Ag

Benoît Pugin

Felix Spindler

Andreas Pfaltz

Marc Thommen

Matthias Lotz

Martin Kesselgruber

Heidi Landert

Björn Gschwend

Weiping Chen

Pierre Martin

Ulrike Nettekoven

Frédéric Maurice Naud

Adrian Wyss

Raphael Aardoom

Markus Müller

Gianpietro Melone

Marc Schönleber

Yann Ribourdouille

Xiangdong Feng

Balamurugan Ramalingam

Felix Spiindler

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.

Bidentate chiral ligands for use in catalytic asymmetric addition reactions

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

Compounds of the formula I in the form of enantiomerically pure diastereomers or a mixture of diastereomers, (I), where the radicals Rare identical or different and are each C-C-alkyl; m is 0 or an integer from 1 to 3; n is 0 or an integer from 1 to 4; Ris a hydrocarbon radical or a C-bonded heterohydrocarbon radical; Cp is unsubstituted or C-C-alkyl-substituted cyclopentadienyl; Y is a C-bonded chiral group which directs metals of metallation reagents into the ortho position; and Phos is a P-bonded P(III) substituent. The compounds are chiral ligands for complexes of transition metals which are used as homogeneous catalysts in asymmetric syntheses. 

Ferrocenediphosphines

Ligands of the formula (I) secondary phosphine-Q-P(&#x2550;O)HR(I) in the form of mixtures of diastereomers or pure diastereomers, in which secondary phosphine is a secondary phosphine group with hydrocarbon radicals or heterohydrocarbon radicals as substituents; Q is a bivalent bisaryl or bisheteroaryl radical with an axial chiral centre to which the two phosphorus atoms are bonded in the ortho positions to the bisaryl or bisheteroaryl bridge bond, or Q is a bivalent ferrocenyl radical with a planar chiral centre or without a planar chiral centre, to which the phosphorus atom of the secondary phosphine is bonded directly or via a C-C-carbon chain to a cyclopentadienyl ring, the &#x2014;P*(&#x2550;O)HRgroup is bonded either on the same cyclopentadienyl ring in ortho position to the bonded secondary phosphine or on the other cyclopentadienyl ring; P* is a chiral phosphorus atom, and Ris a hydrocarbon radical, a heterohydrocarbon radical or a ferrocenyl radical, where Ris a ferrocenyl radical with a planar chiral centre when Q is a ferrocenyl radical without a planar chiral centre. Metal complexes of these ligands are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.

Chiral ligands used in transition metal catalysts for asymmetric addition reactions especially hydrogenation

Abstract Compounds of the formula (I) in the form of racemates, enantiomerically pure diastereomers or a mixture of diastereomers, where the radicals Rare identical or different and are each C-C-alkyl; m is 0 or an integer from 1 to 4; n is 0 or an integer from 1 to 3; p is 0 or an integer from 1 to 5; Ris an aromatic hydrocarbon radical or a C-bonded heterohydrocarbon radical and Ris an aliphatic or C-bonded heteroaliphatic hydrocarbon radical; Rand Rare identical or different and are each an aliphatic or C-bonded heteroaliphatic hydrocarbon radical; Ris an unsubstituted or C-C-alkyl-, C-C-alkoxy- or halogen-substituted hydrocarbon radical; and A is a secondary amino group, are ligands for metal complexes which are suitable as catalysts for homogeneous enantioselective hydrogenation. 

Bis(ferrocenylphosphino) ferrocene ligands used in asymmetric hydrogenation reactions

1,1'-Biphenyl-2,2&#x2032;-diphosphines having at least one amine substituent in the para position relative to the phosphine group and having the formulae are ligands for metal complexes which serve as catalysts for asymmetric addition reactions of prochiral organic compounds and whose catalytic properties can be tailored specifically to particular substrates by substitution of the amine group.

Amine-substituted biphenyldiphosphines

The invention relates to compounds having a structural element of formula (I) in an aromatic hydrocarbon ring, wherein: M represents &#x2014;Li, &#x2014;MgX, (C-C-Alkyl)Sn&#x2014;, &#x2014;ZnXor &#x2014;B(O&#x2014;C-C-Alkyl); Xand X, independent of one another, represent O or N, and C-bound hydrocarbon radicals or heterohydrocarbon radicals are bound to the free bonds of the O and N atoms; group &#x2014;C&#x2550;C&#x2014;, together with C atoms, forms a hydrocarbon aromatic compound and represents XCl, Br or I. The inventive compounds are easily obtained by directly substituting the hydrogen in the ortho position to the P atom with metalation reagents. The metal atoms can then be substituted by a reactive electrophilic compound. The group &#x2014;P(X&#x2014;)(X&#x2014;) - - - -(BH)can then be converted into a secondary phosphine group. The inventive method enables the production of monophosphines and diphosphines even on a large scale, which are valuable ligands for metal complexes serving as catalysts for, e.g. enantioselective hydrogenations. 

Method for producing orthometalated and orthosubstituted metallocenes

The invention relates to compounds of formula (I) provided in the form of racemic compounds, mixtures of diastereomers or essentially pure diastereomers, wherein Rrepresents a hydrogen atom or C-C-alkyl, and at least one secondary phosphine depicts an unsubstituted or substituted cyclic phosphine group, or phosphonium salts thereof having one or two monovalent anions or a divalent anion. The compounds of formula (I) can be obtained by means of a novel method and are valuable ligands for catalytically active metal complexes in asymmetrical synthesis 

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Münchenstein, Switzerland

Benoît Pugin