Solvias Ag

Dsm IP Assets B.v.

Novartis Ag

Andreas Pfaltz

Felix Spindler

Benoît Pugin

Heidi Landert

Matthias Lotz

Frederik Menges

Björn Gschwend

Adrian Wyss

Raphael Aardoom

Joerg R Blankenstein

Werner Bonrath

Thomas Netscher

Jonathan Alan Medlock

Murat Acemoglu

Martin Studer

Benoit Pugin

Stephan Burkhardt

Marc Thommen

Marc-André Mueller

Martin Kesselgruber

Bettina Wüstenberg

Balamurugan Ramalingam

Christian Exner

Marc Schönleber

Xiangdong Feng

Yann Ribourdouille

Claude Schaerer

Bjoern Gschwend

The present invention relates in a first aspect to a process for hydrogenation of ketones having at least a carbon-carbon double bond in the y,8-position to the keto group by hydrogen in the presence of at least one chiral iridium complex of formula (I), where R1 represents a group of formula (II) or (III) or (IV). It has been shown that this process leads to a strong increase in preferential formation of a single isomer. The process is particularly suitable for the hydrogenation of y,8-unsaturated ketones which can be used as flavors and fragrances or for the preparation of vitamin E and its derivatives or of flavors and fragrances. 

Hydrogenation of ketones having at least a carbon-carbon double bond in the &#x3b3;,&#x3b4;-position

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.

The invention relates to the (stereoselective) hydrogenation of carbon-carbon double bonds in compounds having at least one such bond, e.g., isoprenoids, non-cyclic sesquiterpenes, tocomonoenols, tocodienols, tocotrienols or derivatives thereof, as well as to the (stereoselective) hydrogenation of parts/extracts of plant oils containing such tocotrienols or derivatives thereof, in the presence of a chiral Ir complex as the catalyst, whereby preferably one stereoisomer is manufactured in an excess.

Asymmetric hydrogenation of alkenes using chiral iridium complexes

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

Provided is an enantioselective, palladium-catalyzed method for the preparation of &#x3b3;-amino-&#x3b1;,&#x3b2;-unsaturated carboxylic acid derivatives having the formulas II, III, VII and VIII: 

Enantioselective synthesis of &#x3b3;-amino-&#x3b1;&#x3b2;-unsaturated carboxylic acid derivatives

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

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

Process for enantioselectively hydrogenating prochiral ketones to (S)-alcohols using platinum catalysts in the presence of cinchonines or quinidines as modifiers and in the presence of hydrogen, which is characterized in that the modifiers used are cinchonines unsubstituted in the 3-position, 3-ethylidenyl- or 9-methoxycinchonines or derivatives thereof in which the quinoline ring is replaced by other rings.

Hydrogenation of prochiral ketones

Phosphinite-oxazolines and metal complexes

Phosphinite-oxazolines and metal complexes thereof

Growing community of inventors

Binningen, Switzerland

Andreas Pfaltz