Ludwig-maximilians-universitat München

Degussa Aktiengesellschaft

Basf Aktiengesellschaft

Metallgesellschaft Aktiengesellschaft

Degussa - Huls Ag

Other

Basf Corporation

Avecia Limited

Degussa-huels Aktiengesellschaft

Albemarle Germany Gmbh

Ludwig-maximilians-universitaet

Ludwig-maximilians-universitat Muenchen

Munichem Gmbh

Paul Knochel

Arkady L Krasovskiy

Juan Jose Almena Perea

Karlheinz Drauz

Axel Monsees

Ingo Klement

Renat Kadyrov

Thomas Riermeier

Gerard Cahiez

Matthias Lotz

Laure Boymond

Marc Mosrin

Uwe Dingerdissen

Rainer Stürmer

Lothar Laupichler

Sebastian Bernhardt

Boris E Bosch

Christian Lutz

Giuliano Cesar Clososki

Falk Langer

Georg Manolikakes

Dorothée Ziegler

Andrei Gavryushin

Eike Hupe

Mario Rottländer

Stefan Wunderlich

Frank Duebner

Tanja Ireland

Christoph Josef Rohbogner

Felix Kopp

Mario Rottl&auml;nder

Meike Simon

Philip Jones

Valeria Krasovskaya

Gabriele Grossheimann

Vladimir Malakhov

Arkady Krasovskiy

Gliuliano Cesar Clososki

The invention relates to hydrocarbon-soluble halogen or thiolate/magnesium exchange reagents of the general formulaRMgR(OR).LiOR2.(1&#x2212;)LiORDonorin which: Ris a C1-C8 alkyl and ORas well as ORare same or different and represent primary, secondary, or tertiary alkoxide residues having 3 to 18 carbon atoms, wherein Rand/or Rcan for their part contain an alkoxy substituent OR; a assumes a value of 0 to 2, n assumes a value between 0 and 1, and the donor is an organic molecule containing at least 2 nitrogen atoms.

Hydrocarbon-soluble halogen and thiolate/magnesium exchange reagents

Compounds, methods of making the compounds and methods of using the compounds are generally described herein. The compounds are generally of formula RRN&#x2014;ZnY LiY, wherein Rand Rare independently selected from H, aryl, heteroaryl containing one or more heteroatoms, alkyl, alkenyl, alkynyl, and silicon derivatives thereof; and each Y is independently selected from F, Cl, Br, I, CN, SCN, NCO, HalO, HalO, NO, BF, PF, H, an alcoholate of formula OR, a carboxylate of formula RCO; a thiolate of formula SR, RP(O)O, SCOR, SCSR, OSRand NO, wherein n=2 or 3; wherein Ris selected from substituted or unsubstituted aryls or heteroaryls containing 3 to 24 carbon atoms and one or more heteroatoms selected from B, O, N, S, Se, P, linear, branched or cyclic, substituted or unsubstituted alkyls, alkenyls, alkynyls or H; and wherein Hal is a halogen selected from Cl, Br and I.

Production and use of zinc amides

A reagent of the formulaRRN&#x2014;ZnY LiY&#x2003;&#x2003;(I)wherein Rand Rare independently, selected from H, aryl or heteroaryl, linear, branched or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, or silyl derivatives thereof; and Rand Rtogether form part of a cyclic or polymeric structure; Rand/or Ris not H; Y is F, Cl, Br, I, CN, SCN, NCO or HalO, wherein n=3 or 4 and Hal is Cl, Br or I; NO; BF; PF; H; a carboxylate of formula RCO; an alcoholate of formula OR; a thiolate of formula SR; RP(O)O; or SCOR; or SCSR; OSR; wherein n=2 or 3; or NO, wherein n=2 or 3; and a derivative thereof; wherein Ris an aryl or heteroaryl, linear, branched or cyclic, alkyl, alkenyl, alkynyl, or derivatives thereof, or H; or as adduct with a solvent; and preparation and use thereof.

Processes for making an organozinc reagents are disclosed comprising reacting (A) organomagnesium or organozinc complexes with (B) at least one coordination compound comprising one or more carboxylate groups and/or alcoholate groups and/or tertiary amine groups, optionally in combination with zinc ions and/or lithium ions and/or halide ions, wherein the halide ions are selected from chloride, bromide and iodide, the organozinc complex comprises an aryl group, a heteroaryl group or a benzyl group when the coordinating compound is a chelating polyamine, and the reaction is conducted in the presence of zinc complexed with at least one coordinating compound when reactant (A) comprises at least one organomagnesium complex. The resulting organozinc reagents may optionally be isolated from solvents to obtain a solid reagent. The reagents may be used for making organic compounds via Negishi cross-coupling reactions or via aldehyde and/or ketone oxidative addition reactions. The organozinc reagents are stable and, due to their high selectivity, permit maintenance of sensitive functional groups such as aldehydes during cross-coupling.

Organozinc complexes and processes for making and using the same

The present invention relates to zinc amide bases of the general formula (I)(RRN)&#x2014;Zn.MgXLiX&#x2003;&#x2003;(I)wherein Rand Rare each independently selected from substituted or unsubstituted, linear or branched alkyl, alkenyl, alkynyl or silyl derivatives thereof, and substituted or unsubstituted aryl or heteroaryl, and wherein Rand Rcan form together a ring structure, or Rand/or Rcan be part of a polymer structure; Xis a divalent anion or two monovalent anions that are independent from each other; Xis a monovalent anion; a is &#x3e;0; and b is &#x3e;0. The zinc amide bases can be used, amongst other things, for deprotonation and metallization of aromatics.

Bisamide-zinc bases

The present invention relates to anhydrous solutions of MXLiA in a solvent, wherein M is a lanthanide including lanthanum, or yttrium or indium; z&#x3e;0; and X and A are independently or both monovalent anions, preferably Cl, Br or I. The solution is readily prepared by dissolving or suspending MXor its hydrate and z equiv LiA in water or hydrophilic solvents, or mixtures thereof, removing the solvent under vacuum and dissolving the resulting powder in another solvent. The solution of MXLiA can advantageously be used e.g. in addition reactions of Grignard reagents to ketones and imines. Even the catalytic use of MXLiA is possible.

Solutions of anhydrous lanthanide salts and its preparation

The present application relates to mixed Mg/Li amides of the general formula R1R2N&#x2014;Mg(NR3R4)mX,.m zLiY (II) wherein R, R, R, and Rare, independently, selected from H, substituted or unsubstituted aryl or heteroaryl containing one or more heteroatoms, linear, branched or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, or silyl derivatives thereof; and Rand Rtogether, or Rand Rtogether can be part of a cyclic or polymeric structure; and wherein at least one of Rand Rand at least one of Rand R is other than H; X and Y are, independently, selected from the group consisting of F; Cl; Br; I; CN; SCN; NCO; HaIO, wherein n=3 or 4 and Hal is selected from Cl, Br and I; NO; BF; PF; H; a carboxylate of the general formula RCO; an alcoholate of the general formula ORX; a thiolate of the general formula SR; RP(O)O; or SCOR; or SCSR; OSR, wherein n=2 or 3; or NO, wherein n=2 or 3; and a derivative thereof; wherein Ris a substituted or unsubstituted aryl or heteroaryl containing one or more heteroatoms, linear, branched or cyclic, substituted or unsubstituted alkyl, alkenyl, alkynyl, or derivatives thereof, or H; m is O or 1; and z&#x3e;O; as well as a process for the preparation of the mixed Mg/Li amides and the use of these amides, e.g. as bases.

Preparation and use of magnesium amides

The present invention is directed to a reagent for use in the preparation of organomagnesium compounds as well as to a method of preparing such organomagnesium compounds. The present invention furthermore provides a method of preparing functionalized or unfunctionalized organic compounds as well as the use of the reagents of the present invention in the preparation of organometallic compounds and their reaction with electrophiles. Finally, the present invention is directed to the use of lithium salts&#x2014;LiY in the preparation of organometallic compounds and their reactions with electrophiles and to an organometallic compound which is obtainable by the disclosed method.

Method of preparing organomagnesium compounds

The present invention concerns novel unsymmetrical chiral diphosphines of a mixed aliphatic-aromatic type and processes for synthesizing them, complexes of these compounds and their use as catalysts.

Cycloaliphatic/aromatic diphosphines and use thereof in catalysis

The invention relates to ferrocenyl ligands of general formula (II), the S,S-enantiomer or the R,R-enantiomer of the ferrocenyl ligands of formula (II) being enriched, and a method for producing such ligands.

Ferrocenyl ligands and method for the production of such ligands

The invention relates to bidentate organophosphorous ferrocenyl ligands containing ligands of formula (I), to their complex compounds and to their utilization in catalytic processes.

Ferrocenyl ligands and the use thereof in catalysis

The invention relates to a process for preparing Grignard compounds of the formula I. The invention additionally relates to compounds of the formula I and to polymer-bound compounds of the formula Ia. The invention further relates to the use of the process for preparing substance libraries and to the use of the compounds of the formulae I and Ia in chemical synthesis.

Method for producing Grignard compounds

An allylic compound is reacted with an organozinc compound Zn(R ) to eliminate a group (the leaving group) from the allylic compound and to add a group from the organozinc compound to it in the presence of a copper salt catalyst and a chiral organic ligand for the copper. A novel ferrocenyl compound and a novel copper complex of the ferrocenyl compound and copper are also described.

Copper-catalyzed enantioselective allylic substitution reactions

A process for the stereoselective preparation of Grignard compounds of the formula I and polymer-bonded compounds of the formula Ia is described. The process can be used for producing substance reference libraries and the compounds of the formulae I and Ia can be used in stereoselective chemical synthesis.

Method for the stereoselective production of grignard compounds and use thereof

Growing community of inventors

Munich, Germany

Paul Knochel