| 摘要 |
#CMT# #/CMT# New chiral phosphorus ligands comprising a substituted benzene ring with a phosphino group and a phosphinoamino group on adjacent ring carbons, each further substituted on the phosphorus atoms with chiral or achiral organic residues. #CMT# : #/CMT# Chiral phosphorus ligands of formula (I) are new. R 1>, R 2>, R 7>, R 8>chiral or achiral residues derived from optionally substituted, optionally functionalised, linear, branched or cyclic aliphatic or aromatic groups (optionally linked together); R 3>-R 6>H, halogen, or groups as defined above for R 1>etc. Independent claims are included for (1) a method for the production of (I) by reacting an o-halogenated phenylamine (IX) with a phosphorus component (X) to give an o-aminophenylphosphine (XI) and then reacting (XI) with another phosphorus component (XII) (2) a method of enantioselective catalysis with a catalyst composition containing (I), in which the composition is prepared in situ by mixing the components or is present as a preformed complex. #CMT#[Image]#/CMT# #CMT#USE : #/CMT# For the transition metal-catalysed enantioselective hydrogenation, hydroboration, hydrosilylation, hydrovinylation, isomerisation, hydrocyanation and/or hydroformylation of organic compounds, especially for the iridium-catalysed hydrogenation of prochiral unsaturated compounds (especially imines and quinolines) and for the rhodium- or ruthenium-catalysed hydrogenation of prochiral unsaturated compounds (claimed). #CMT#ADVANTAGE : #/CMT# New, modular, chiral phosphorus ligands, especially for use in hydrogenation catalysts, characterised by ease of production and handling, high enantioselectivity, good activity and the possibility of wide structural variation for optimising catalysts in industrial application. #CMT#ORGANIC CHEMISTRY : #/CMT# Preferred Complexes: Complexes of (I) with transition metals, especially iridium, rhodium and ruthenium, as catalyst components. Preferred Method: Reaction as above, in which (IX) is an o-halogenated arylamine (preferably with fluorine as the halogen), (X) is a phosphide salt and (XII) is a monohalogenated organophosphorus compound. #CMT#DEFINITIONS : #/CMT# Preferred Definitions: R 1>, R 2>, R 7>, R 8>methyl, ethyl, n- or iso-propyl, n- or tert.-butyl, pentyl, hexyl, fluoroalkyl, fluoroalkylphenyl, phenyl, chlorophenyl, tolyl, anisyl, trifluoromethylphenyl, dimethylphenyl, benzyl, xylyl, fluorenyl, cyclohexyl, menthyl, allyl, hydroxyphenyl, pentafluorophenyl, carboxyphenyl, naphthyl, pyridyl, furyl, bis-(trifluoromethyl)-phenyl, pyrrolyl, pyrrolidinyl, binaphthylene, biphenylene, 2,2',3,3'-tetrahydro-1,1'-spirobi[indene]-7,7'-diyl, 2,2'-(2,2-dimethyl-1,3-dioxolane-4,5-diyl)-dipropan-2-yl, 1,2-phenylene, 1,2-cyclohexylene or groups of formula (II)-(VIII); X : O, S, NR 32>or -(CH 2) p-; p : 0-5; s : 1-3; R 10>-R 32>H, halogen or groups as defined for R 1>etc.; preferably, R 1>and/or R 2>aryl (especially phenyl) attached to the central structure via -(CH 2) q- or via groups such as ether, thioether, ester, thioester, acyl or amino groups; q : 0-5; preferably, R 7>, R 8>groups of formula (XIII)-(XV), especially 1,1'-binaphth-2,2'-dioxy; R 33>-R 35>as for R 10>-R 32>; R 3>-R 5>H, halogen, or optionally chiral 1-18C alkyl (aliphatic or alicyclic), aryl, ether, thioether, ester, acid, amino, sulfoxide, sulfonyl, phosphanoyl, phosphoryl, amido, guanidino, nitro or heterocyclic residues; R 6>H, halogen, methyl, ethyl, propyl, butyl, hexyl, benzyl, cyclohexyl, allyl, phenyl, methylphenyl, chlorophenyl or tolyl; R 9>H or an optionally chiral group, preferably a group with a chirality center in the alpha position, especially 1-pheneth-1-yl, 1-(1- or 2-naphthyl)-eth-1-yl, but-2-yl, 3,3-dimethylbut-2-yl, 3-methylbut-2-yl, 1-indanyl or 1,2,3,4-tetrahydronaphth-1-yl. #CMT#[Image]#/CMT# #CMT#[Image]#/CMT# #CMT#[Image]#/CMT# #CMT#[Image]#/CMT# #CMT#[Image]#/CMT# #CMT#EXAMPLE : #/CMT# A solution of 991 mg N-((S)-alpha -methylbenzyl)-2-diphenyl-phosphinoamine in 10 ml THF was mixed with 0.4 ml TMEDA, cooled to -70[deg] C, treated with 2.6 mmols (1.3 ml) n-butyl-lithium, stirred for 2 hours, treated with a solution of 1.015 g (R)-4-chloro-3,5-dioxa-4-phosphacyclohepta[2,1-a;3,4-a']-dinaphthalene in 8 ml THF, slowly heated to room temperature (RT), stirred for 3 hours and worked up by removal of solvent, dissolution in toluene, filtration through alumina, removal of toluene and recrystallisation from dichloromethane (DCM)/pentane. This gave 890 mg (49%) (S,S)-(3,5-dioxa-4-phospha-cyclohepta[2,1-a;3,4-a']dinaphthalen-4-yl)-(2-diphenylphosphanyl-phenyl)-(1-phenyl-ethyl)-amine (ligand 2) (characterised by 1>H-NMR, 13>C( 1>H)-NMR, 31>P-NMR and MS analysis). A solution of 0.025 mmol ligand 2 in 5 ml DCM was added to a solution of 0.025 mmol rhodium complex salt (Rh[COD] 2BF 4) in 5 ml DCM, then 2 ml of the resulting stock solution was diluted with 8 ml DCM. The final solution (2 ml) was transferred to a high-pressure reactor containing 1 mmol dimethyl itaconate, then the mixture was diluted with 1 ml DCM, pressurised to 10 bar with hydrogen and stirred at RT for 30 minutes. This gave dimethyl methylsuccinate with a conversion of more than 99.9% and an enantiomeric excess of 99.6%. |
