Chiral diphosphorus compounds and their transition metal complexes

Abstract

The present invention relates to chiral diphosphorus compounds and their transition metal complexes, to a process for preparing chiral diphosphorus compounds and their transition metal complexes and also to their use in asymmetric syntheses.

1 . Compounds selected from the group consisting of 2,3-bis-O-(Diphenylphosphino)-1,6-di-O-(triphenylmethyl)-2,5-anhydro-D-mannitol, 2,3-bis-O-(diphenylphosphino)-1,6-dideoxy-2,5-anhydro-D-mannitol, 2,3-bis-O-(diphenylphosphino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitol, 2,3-bis-O-(diphenyl-phosphino)-1,6-di-O-(triphenylmethyl)-2,5-anhydro-L-iditol, 2,3-bis-O-(diphenylphosphino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-L-iditol, 2,3-bis-O-(diphenylphosphino)-1,6-dideoxy-2,5-anhydro-L-iditol, 2,3-bis-O-(di(4-methoxyphenyl)phosphino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitol, 2,3-bis-O-(di((4-Trifluoromethyl)phenyl)phosphino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-an-hydro-D-mannitol, 2-O-(di(2,4-dimethylphenyl)phosphino)-3-O-(diphenyl-phosphino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitol, 2-O-(di(2,4-dimethylphenyl)phosphino)-3-O-(4,8-ditert-butyl-2,10-dimethyl-12H-dibenzo-[δ,γ][1,3,2] dioxaphosphocino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitol and 2-O-(di(2,4-dimethylphenyl)phosphino)-3-O-(2,10-dimethyl-4,8-bis(1-methylcyclohexyl)-12H-dibenzo[δ,γ]-[1,3,2]dioxaphosphocino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitol.  
   
   
       2 . Compounds of the formula (XXa)  
     
       
         
         
             
             
         
       
     
     wherein, 
 R 1  and R 2  may each independently be: hydrogen, C 1 -C 20 -alkyl, C 1 -C 20 -fluoroalkyl, C 2 -C 20 -alkenyl, C 4 -C 24 -aryl, C 5 -C 25 -arylalkyl, C 6 -C 26 -aryl-alkenyl or NR 7 R 8 , OR , —(C 1 -C 8 -alkyl)-OR 8 , —(C 1 -C 8 -alkyl)-NR 7 R 8  or —O 2 CR 8  where R 7  and R 8  are each independently C 1 -C 8 -alkyl, C 5 -C 14 -arylalkyl or C 4 -C 15 -aryl, or R 7  and R 8  together are a cyclic amino radical having a total of 4 to 20 carbon atoms,  
 or R 1  and R 2  are each independently radicals of the formula (II)  
   —R 9 —SiR 10 R 11 R 12    (II)  
 where  
 R 9  is absent, or is oxygen or methylene and  
 R 10 , R 11  and R 12  are each independently C 1 -C 12 -alkyl, C 5 -C 15 -arylalkyl or C 4 -C 14 -aryl.  
 
   
   
       3 . Transition metal complexes containing compounds comprising compounds of the formula (I),  
     
       
         
         
             
             
         
       
       where  
       *1, *2, *3 and *4 are each independently a stereogenic carbon atom which is in the R- or S-configuration,  
       X 1  and X 2  are each independently absent or are oxygen and  
       R 1  and R 2  may each independently be: hydrogen, C 1 -C 20 -alkyl, C 1 -C 20 -fluoroalkyl, C 2 -C 20 -alkenyl, C 4 -C 24 -aryl, C 5 -C 25 -arylalkyl, C 6 -C 26 -aryl-alkenyl or NR 7 R 8 , OR 8 , —(C 1 -C 8 -alkyl)-OR , —(C 1 -C 8 -alkyl)-NR 7 R 8  or —O 2 CR 8  where R 7  and R 8  are each independently C 1 -C 8 -alkyl, C 5 -C 14 -arylalkyl or C 4 -C 15 -aryl, or R 7  and R 8  together are a cyclic amino radical having a total of 4 to 20 carbon atoms,  
       or R 1  and R 2  are each independently radicals of the formula (II)  
         —R 9 —SiR 10 R 11 R 12    (II)  
       where  
       R 9  is absent, or is oxygen or methylene and  
       R 10 , R 11  and R 12  are each independently C 1 -CO 2 -alkyl, C 5 -C 15 -arylalkyl or C 4 -C 14 -aryl and  
       R 3 , R 4 , R 5  and R 6  are each independently R 13 , OR 14  or NR 5 R 16  where R 13 , R 14 , R 15  and R 16  are each independently C 1 -C 12 -alkyl, C 5 -C, 5 -arylalkyl or C 4 -C 14 -aryl, or NR 15 R 16  together is a cyclic amino radical having 4 to 20 carbon atoms, or R 3  and R 4  and/or R 5  and R 6  in each case together are —O—R 17 —O— where R 17  is a radical selected from the group of C 2 -C 4 -alkylene, 1,2-phenylene, 1,3-phenylene, 1,2-cyclohexylene, 1,1′-ferrocenylene, 1,2-ferrocenylene, 2,2′-(1,1′-binaphthylene), 2,2′-(1,1′)-biphenylene and 1,1′-(diphenyl-2,2′-methylene)-diyl, and the radicals mentioned may optionally be mono- or polysubstituted by radicals selected from the group of fluorine, chlorine, C 1 -C 8 -alkoxy and C 1 -C 8 -alkyl.  
     
   
   
       4 . Transition metal complexes according to  claim 3 , wherein the transition metal is ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum and/or copper.  
   
   
       5 . Transition metal complexes according to  claim 3 , wherein the molar ratio of transition metal to compounds of Formula 1 is 1:1.  
   
   
       6 . Transition metal complexes according to  claim 4 , wherein the metal complexes follow formula (XXIII)  
       [(I)L 1   2 M]  (XXIII)  where (I) represents a compound of the formula (I) as defined in  claim 3  and    M is rhodium or iridium and    L 1  is in each case a C 2 -C 12 -alkene or a nitrile or    L 1   2  together is a (C 4 -C 12 )-diene.    
   
   
       7 . Compounds comprising: [Rh(cod)(2,3-bis-O-(diphenylphosphino)-1,6-di-O-(triphenylmethyl)-2,5-anhydro-D-mannitol)]BF 4 , [Rh(cod)(2,3-bis-O-(diphenylphos-phino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitol)]BF 4 , [Rh(cod)(2,3-bis-O-(diphenylphosphino)-1,6-dideoxy-2,5-anhydro-D-mannitol)]BF 4  and/or [Ir(cod)(2,3-bis-O-(diphenylphos-phino)-1,6-di-O-(tert-butyldiphenylsilyl)-2,5-anhydro-D-mannitol)]BF 4 .  
   
   
       8 . Transition metal complexes according to  claim 3 , characterized in that they are obtained by reacting transition metal compounds and compounds comprising compounds of the formula (I),  
     
       
         
         
             
             
         
       
       where  
       *1, *2, *3 and *4 are each independently a stereogenic carbon atom which is in the R- or S-configuration,  
       X 1  and X 2  are each independently absent or are oxygen and  
       R 1  and R 2  may each independently be: hydrogen, C 1 -C 20 -alkyl, C 1 -C 20 -fluoroalkyl, C 2 -C 20 -alkenyl, C 4 -C 24 -aryl, C 5 -C 25 -arylalkyl, C 6 -C 26 -aryl-alkenyl or NR 7 R 8 , OR 8 , —(C 1 -C 8 -alkyl)-OR 8 , —(C 1 -C 8 -alkyl)-NR 7 R 8  or —O 2 CR 8  where R 7  and R 8  are each independently C 1 -C 8 -alkyl, C 5 -C 14 -arylalkyl or C 4 -C 15 -aryl, or R 7  and R 8  together are a cyclic amino radical having a total of 4 to 20 carbon atoms,  
       or R 1  and R 2  are each independently radicals of the formula (II)  
         —R 9 —SiR 10 R 11 R 12    (II)  
       where  
       R 9  is absent, or is oxygen or methylene and  
       R 10 , R 11  and R 12  are each independently C 1 -C 12 -alkyl, C 5 -C 15 -arylalkyl or C 4 -C 14 -aryl and  
       R 3 , R 4 , R 5  and R 6  are each independently R 13 , OR 14  or NR 15 R 16  where R 13 , R 14 , R 15  and R 16  are each independently C 1 -C 12 -alkyl, C 5 -C 15 -arylalkyl or C 4 -C 14 -aryl, or NR 15  R 16  together is a cyclic amino radical having 4 to 20 carbon atoms, or R 3  and R 4  and/or R 5  and R 6  in each case together are —O—R 17 —O— where R 17  is a radical selected from the group of C 2 -C 4 -alkylene, 1,2-phenylene, 1,3-phenylene, 1,2-cyclohexylene, 1,1′-ferrocenylene, 1,2-ferrocenylene, 2,2′-(1,1′-binaphthylene), 2,2′-(1,1′)-biphenylene and 1,1′-(diphenyl-2,2′-methylene)-diyl, and the radicals mentioned may optionally be mono- or polysubstituted by radicals selected from the group of fluorine, chlorine, C 1 -C 8 -alkoxy and C 1 -C 8 -alkyl.  
     
   
   
       9 . Transition metal complexes according to  claim 8 , characterized in that the transition metal compounds comprise: 
 transition metal compounds of the formula (XXIIa)      M(An 1 ) q    (XXIIa)    where    M is rhodium, iridium, ruthenium, nickel, palladium, platinum or copper and    An 1  is chloride, bromide, acetate, nitrate, methanesulphonate, trifluoromethanesulphonate or acetylacetonate and    q is 3 for rhodium, iridium and ruthenium, is 2 for nickel, palladium and platinum, and is 1 for copper,    or transition metal compounds of the formula (XXIIb),      M(An 2 ) q L 1   2    (XXIIb)    where    M is rhodium, iridium, ruthenium, nickel, paladium, platinum or copper and    An 2  is chloride, bromide, acetate, methanesulphonate or trifluoromethanesulphonate, tetrafluoroborate or hexafluorophosphate, perchlorate, hexafluoroantimonate, tetra(bis-3,5-trifluromethylphenyl)borate or tetraphenylborate and    q is 1 for rhodium and iridium, is 2 for ruthenium, nickel, palladium and platinum, and is 1 for copper,    L 1  is in each case a C 2 -C 12  alkene or    L 1   2  together is a (C 4 -C 12 )-diene    or transition metal compounds of the formula (XXIIc)      [ML 2 An 1   2 ] 2    (XXIIc)    where    M is ruthenium and    L 2  is an aryl radical or cyclooctadiene, norbornadiene or methylallyl    or transition metal compounds of the formula (XXIId)      Met 3   q [M(An 3 ) 4 ]  (XXIId)    where    M is palladium, nickel, iridium or rhodium and    An 3  is chloride or bromide and    Met 3  is lithium, sodium, potassium, ammonium or organic ammonium and    q is 3 for rhodium and iridium, and is 2 for nickel, palladium and platinum,    or transition metal compounds of the formula (XXIIe)      [M(L 3 ) 2 ]An 4    (XXIIe)    where    M is iridium or rhodium and    L 3  is (C 4 -C 12 )-diene and    An 4  is a noncoordinating or weakly coordinating anion or    Ni(1,5-cyclooctadiene) 2 , Pd 2 (dibenzylideneacetone) 3 , Pd[PPh 3 ] 4 , cyclopentadienyl 2 Ru, Rh(acac)(CO) 2 , Ir(pyridine)2(1,5-cyclo-octadiene), Cu(phenyl)Br, Cu(phenyl)Cl, Cu(phenyl)I, Cu(PPh3) 2 Br, [Cu(CH 3 CN) 4 ]BF 4  and [Cu(CH 3 CN) 4 ]PF 6  or multinuclear bridged complexes, for example [Rh(1,5-cyclooctadiene)Cl] 2 , [Rh(1,5-cyclooctadiene)Br] 2 , [Rh(ethene) 2 Cl] 2  or [Rh(cyclooctene) 2 Cl] 2 .    
   
   
       10 . Transition metal complexes according to  claim 9 , wherein the transition metal compounds comprise: [Rh(cod)Cl] 2 , [Rh(cod)Br] 2 , [Rh(cod) 2 ]ClO 4 , [Rh(cod) 2 ]BF 4 , [Rh(cod) 2 ]PF 4 , [Rh(cod) 2 ]ClO 6 , [Rh(cod) 2 ]OTf, [Rh(cod) 2 ]BAr 4  (Ar=3,5-bistrifluoromethylphenyl), [Rh(cod) 2 ]SbF 6 , RuCl 2 (cod), [(cymene)RUCl 2 ] 2 , [(benzene)RuCl 2 ] 2 , [(mesityl)RUCl 2 ] 2 , [(cymene)RuBr 2 ] 2 , [(cymene)Rul 2 ] 2 , [(cymene)Ru(BF 4 ) 2 ] 2 , [(cymene)Ru(PF 6 ) 2 ] 2 , [(cymene)Ru(BAr 4 ) 2 ] 2  (Ar=3,5-bistrifluoromethylphenyl), [(cymene)Ru(SbF 6 ) 2 ] 2 , [Ir(cod)Cl] 2 , [Ir(cod) 2 ]PF 6 , [Ir(cod) 2 ]ClO 4 , [Ir(cod) 2 ]SbF 6 , [Ir(cod) 2 ]BF 4 , [Ir(cod) 2 ]OTf, [Ir(cod) 2 ]BAr 4  (Ar=3,5-bistrifluoromethylphenyl), RuCl 3 , NiCl 3 , RhCl 3 , PdCl 2 , PdBr 2 , Pd(OAc)2, Pd 2 (dibenzylideneacetone) 3 , Pd(acetylacetonate) 2 , CuOTf, Cul, CuCl, Cu(OTf) 2 , CuBr, Cul, CuBr 2 , CuCl , Cul   2 , [Rh(nbd)Cl] 2 , [Rh(nbd)Br] 2 , [Rh(nbd) 2 ]ClO 4 , [Rh(nbd) 2 ]BF 4 , [Rh(nbd) 2 ]PF 6 , [Rh(nbd) 2 ]OTf, [Rh(nbd) 2 ]BAr 4  (Ar=3,5-bistrifluoromethylphenyl), [Rh(nbd) 2 ]SbF 6 , RuCl 2 (nbd), [Ir(nbd) 2 ]PF 6 , [Ir(nbd) 2 ]ClO 4 , [Ir(nbd) 2 ]SbF 6 , [Ir(nbd) 2 ]BF 4 , [Ir(nbd) 2 ]OTf, [Ir(nbd) 2 ]BAr 4  (Ar=3,5-bistrifluoromethylphenyl), Ir(pyridine) 2 (nbd), [Ru(DMSO) 4 Cl 2 ], [Ru(CH 3 CN) 4 Cl 2 ], [Ru(PhCN) 4 Cl 2 ], [Ru(cod)Cl 2 ] n , [Ru(cod) 4 (methallyl) 2 ], [Ru(acetylacetonate) 3 ].  
   
   
       11 . Transition metal complexes according to  claim 10 , wherein transition metal compounds comprise: 
 [Rh(cod)Cl] 2 , [Rh(cod)Br] 2 , [Rh(cod) 2 ]ClO 4 , [Rh(cod) 2 ]BF 4 , [Rh(cod) 2 ]PF 4 , [Rh(cod) 2 ]ClO 6 , [Rh(cod) 2 ]OTf, [Rh(cod) 2 ]BAr 4  (Ar=3,5-bistrifluoromethylphenyl), [Rh(cod) 2 ]SbF 6 , [Rh(nbd)Cl] 2 , [Rh(nbd)Br] 2 , [Rh(nbd) 2 ]ClO 4 , [Rh(nbd) 2 ]BF 4 , [Rh(nbd) 2 ]PF 6 , [Rh(nbd) 2 ]OTf, [Rh(nbd) 2 ]BAr 4  (Ar=3,5-bistrifluoromethylphenyl), [Rh(nbd) 2 ]SbF 6 , [Ir(cod)Cl] 2 , [Ir(cod) 2 ]PF 6 , [Ir(cod) 2 ]ClO 4 , [I r(cod) 2 ]SbF 6 , [Ir(cod) 2 ]BF 4 , [I r(cod) 2 ]OTf, [I r(cod) 2 ] BAr 4  (Ar=3,5-bistrifluoromethylphenyl).    
   
   
       12 . Transition metal complexes according to  claim 7 , wherein the amount of the transition metal compounds used is 25 to 200 mol %, based on the compound according to  claim 3 .  
   
   
       13 . A process for preparing stereoisomerically enriched compounds comprising providing transition metal complexes of  claim 3 .  
   
   
       14 . The process according to  claim 13 , wherein stereoisomerically enriched compounds are obtained by asymmetric 1,4-additions, asymmetric hydroformylations, asymmetric hydrocyanations, asymmetric Heck reactions and asymmetric hydrogenations.  
   
   
       15 . A process for preparing active ingredients in pharmaceuticals and agrochemicals, or intermediates of these two classes comprising providing stereoisomerically enriched compounds of  claim 12 .  
   
   
       16 . A process for catalyzing reactions comprising providing metal complexes according to  claim 3 .  
   
   
       17 . Process for preparing stereoisomerically enriched compounds by catalytic hydrogenations of olefins, enamines, enamides, imines or ketones, 1,4-additions, hydroformylations, hydrocyanations or Heck reactions, comprising providing catalysts comprising transition metal complexes according to  claim 3 .  
   
   
       18 . Process according to  claim 16 , wherein the amount of the transition metal complexes used is 0.001 to 5 mol %, based on the weight of the substrate.  
   
   
       19 . Process according to  claim 17 , wherein the stereoisomerically enriched compounds are obtained by catalytic hydrogenation of olefins, enamides or imines.  
   
   
       20 . Process according to  claim 16 , wherein the working temperature is −20° C. to 200° C.  
   
   
       21 . Process according to  claim 18 , wherein the hydrogen pressure is 0.1 to 200 bar.  
   
   
       22 . Catalysts comprising transition metal complexes according to  claim 3.