CN100410263C - 作为均相氢化催化剂的取代的二茂铁基二膦 - Google Patents
作为均相氢化催化剂的取代的二茂铁基二膦 Download PDFInfo
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- CN100410263C CN100410263C CNB2004800125336A CN200480012533A CN100410263C CN 100410263 C CN100410263 C CN 100410263C CN B2004800125336 A CNB2004800125336 A CN B2004800125336A CN 200480012533 A CN200480012533 A CN 200480012533A CN 100410263 C CN100410263 C CN 100410263C
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- 239000003446 ligand Substances 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 title abstract description 13
- 238000009905 homogeneous catalytic hydrogenation reaction Methods 0.000 title abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- -1 C6-C10aryi or C7-C11 Chemical group 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 14
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 150000004696 coordination complex Chemical class 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 18
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- 239000002253 acid Substances 0.000 claims description 17
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 17
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- 239000010948 rhodium Substances 0.000 claims description 15
- 238000005984 hydrogenation reaction Methods 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 12
- 229910052741 iridium Inorganic materials 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 229910052703 rhodium Inorganic materials 0.000 claims description 12
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
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- 238000007872 degassing Methods 0.000 description 4
- CCRCUPLGCSFEDV-BQYQJAHWSA-N methyl trans-cinnamate Chemical compound COC(=O)\C=C\C1=CC=CC=C1 CCRCUPLGCSFEDV-BQYQJAHWSA-N 0.000 description 4
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
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- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
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- ULNVTMFBEVVUMH-UHFFFAOYSA-N P.[Cl] Chemical compound P.[Cl] ULNVTMFBEVVUMH-UHFFFAOYSA-N 0.000 description 1
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
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- KFGVRWGDTLZAAO-UHFFFAOYSA-N cyclopenta-1,3-diene dicyclohexyl(cyclopenta-1,3-dien-1-yl)phosphane iron(2+) Chemical compound [Fe++].c1cc[cH-]c1.C1CCC(CC1)P(C1CCCCC1)c1ccc[cH-]1 KFGVRWGDTLZAAO-UHFFFAOYSA-N 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
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- 125000000623 heterocyclic group Chemical group 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
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- 238000006460 hydrolysis reaction Methods 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical compound OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 description 1
- OPUAWDUYWRUIIL-UHFFFAOYSA-N methanedisulfonic acid Chemical compound OS(=O)(=O)CS(O)(=O)=O OPUAWDUYWRUIIL-UHFFFAOYSA-N 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- WSDQIHATCCOMLH-UHFFFAOYSA-N phenyl n-(3,5-dichlorophenyl)carbamate Chemical compound ClC1=CC(Cl)=CC(NC(=O)OC=2C=CC=CC=2)=C1 WSDQIHATCCOMLH-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
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- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
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- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DPKBAXPHAYBPRL-UHFFFAOYSA-M tetrabutylazanium;iodide Chemical compound [I-].CCCC[N+](CCCC)(CCCC)CCCC DPKBAXPHAYBPRL-UHFFFAOYSA-M 0.000 description 1
- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
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- C—CHEMISTRY; METALLURGY
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- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0286—Complexes comprising ligands or other components characterized by their function
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Abstract
式(I)的化合物是用于含有双键的前手性有机化合物的均相氢化催化剂的金属络合物的配体,其中R1是C1-C4烷基、C6-C10芳基或C7-C11芳烷基,R2是开链或环仲氨基,并且R是式(II)的基团,其中R3是C1-C4烷基或C1-C4烷氧基,并且R4是H、C1-C4烷基或C1-C4烷氧基。使用所述催化剂可以取得非常高的活性、生产率以及对映体选择性。
Description
本发明涉及作为用于均相氢化催化剂的配体的在膦基上具有3,5-或3,4,5-取代的苯基的2,2′-双(α-仲氨基烷基)-1,1′-二膦基二茂铁;这些配体与元素周期表第8族过渡金属的金属络合物;和氢化前手性烯键式不饱和有机化合物的方法。
EP-A-0967015一般性地描述了在2,2′位上被非常不同的手性α-取代的烷基取代的1,1′-二膦基二茂铁。具体提及了一些在2,2′位上被α-仲氨基苯基甲基例如α-二甲基氨基苯基甲基取代的1,1′-二苯基膦基二茂铁。这些二膦基二茂铁可以作为用于碳-碳或碳-杂原子双键的氢化的有效的均相和对映体选择性金属催化剂。但没有提及在两个膦基中苯基取代的可能影响。
目前令人惊奇地发现,两个膦基中苯基的3、5和可能4位的特定取代产生这样的配体,所述配体的金属络合物显示相当高的活性并因此使氢化产物的生产率得以提高,并且在前手性烯键式不饱和化合物的氢化中还显示出非常高的对映体选择性,这样氢化甚至就可以在大气压力下进行。因此,使用这样的金属络合物的氢化方法,可以提供显著的工艺技术和经济优点。
本发明提供了基本上纯对映体形式的式I化合物,
其中
R1是C1-C4烷基、C6-C10芳基或C7-C11芳烷基,
R2是开链或环状仲氨基,
并且R是下式的基团
其中
R3是C1-C4烷基或C1-C4烷氧基,并且
R4是H、C1-C4烷基或C1-C4烷氧基。
C1-C4烷基R1可以是直链或支链的,并且可以是甲基、乙基、正丙基或异丙基和正丁基、异丁基或叔丁基。所述烷基优选是直链的。优选的烷基R1是甲基和乙基。
C6-C10芳基R1可以是例如苯基或萘基。优选的芳基R1是苯基。
优选的芳烷基R1是苄基。
在一个优选的实施方案中,式I化合物中的R1是苯基。
仲氨基优选含有总共2-16个碳原子,更优选2-12个碳原子,而特别优选2-6个碳原子。
开链或环状仲氨基R2可以符合式R5R6N-,其中R5和R6分别彼此独立地是C1-C6烷基,优选C1-C4烷基,C3-C8环烷基,优选C5-C6环烷基,C6-C10芳基,优选苯基,或C7-C11芳烷基,优选苄基,其中环烷基和芳基是未取代的或被C1-C4烷基或C1-C4烷氧基取代,或者R5与R6一起形成四亚甲基、五亚甲基或3-氧杂亚戊基。优选为直链的烷基的实例是甲基、乙基、丙基和丁基。环烷基的实例是环戊基、环己基和环辛基。
在一个优选的实施方案中,R5与R6分别是甲基、乙基、苯基、苄基、环己基,或者R5与R6一起形成四亚甲基、五亚甲基或3-氧杂亚戊基。特别优选R5和R6分别是甲基。
烷基和烷氧基R3可以是直链或支链的,并且可以是甲基、乙基、正丙基或异丙基和正丁基、异丁基或叔丁基,或甲氧基、乙氧基、正丙氧基或异丙氧基和正丁氧基、异丁氧基或叔丁氧基。优选的烷基是甲基和叔丁基。优选的烷氧基是甲氧基和叔丁氧基。
在一个优选的实施方案中,两个基团R3都是甲基、叔丁基或甲氧基。
烷基或烷氧基R4可以是直链或支链的。已经给出了关于R3的具体实例。
在一个优选的实施方案中,R4是H或甲氧基。
特别优选的式I化合物是定义如下的那些:其中R1是苯基,R2是二-C1-C4烷基氨基、特别是二甲基氨基,R3是甲基、叔丁基或甲氧基,并且R4是H、甲基或甲氧基。
式I化合物可以通过例如描述于EP-A 0 965 574中的已知方法,或者通过J.J.Almena Perea在“Tetrahedron:Asymmetry”10(1999),375-384页中描述的方法获得。例如,所述化合物可以这样获得:将式II化合物
其中
R1就R2具有关于式I化合物所给出的含义,并且X是H、Cl、Br或I,优选H或Br,
与有机金属化合物例如烷基锂(甲基锂或丁基锂)反应并随后加入式III的一卤代膦
X1-P(R)2 (III),
其中
R如上面所定义,X1是卤素,优选Cl、Br或I。
式II和是III化合物是已知的,或者可以通过类似的方法制备。反应通常在惰性溶剂例如醚或烃中进行。有关该反应的更为详细的描述参见实施例。取代的卤代膦的制备对于本领域的技术人员是已知的,并且可以通过出版的制备方法或者通过类似方法从适当取代的芳基溴原料制备。
式I的新化合物是选自第TM8族金属,特别是选自Ru、Rh和Ir的金属的络合物的配体,所述络合物是用于不对称合成例如前手性烯键式不饱和有机化合物的不对称氢化的极好的催化剂或催化剂前体。所述金属络合物显示非常高的活性和对映体选择性。如果使用前手性不饱和有机化合物,在有机化合物的合成中可以导致非常高的旋光异构体过量,并且可以在短的反应时间内取得高的化学转化率。对选择的底物的活性和对映体选择性显著高于用已知的未取代的二膦获得的活性和对映体选择性。另外,通过所述金属络合物,还可以使生产率得到显著提高。这样,甚至可以在大气压下进行有效的氢化过程。
本发明还提供了选自第TM8族金属的金属与作为配体的式I化合物的络合物。
可以使用的金属有例如Cu、Ag、Au、Ni、Co、Rh、Pd、Ir、Ru和Pt。优选的金属是铑和铱以及钌、铂和钯。
特别优选的金属是钌、铑和铱。
根据金属原子的氧化值和配位数,金属络合物还可以包含配体和/或阴离子。它们也可以是阳离子金属络合物。这样的类似的金属络合物及其制备方法被广泛描述于有关文献中。
所述金属络合物可以例如符合式IV和V,
A1MeLn (IV), (A1MeLn)Z+(E-)Z (V),
其中A1是式I化合物,
基团L是相同或不同的单齿阴离子或非离子配体,或者基团L是相同或不同的二齿阴离子或非离子配体;
当L是单齿配体时n是2、3或4,或者当L是二齿配体时n是1或2;
z是1、2或3;
Me是选自Rh和Ir的金属;所述金属具有氧化态0、1、2、3或4;
E-是含氧酸或配酸的阴离子;并且
阴离子配体与金属的1、2、3或4氧化态的电荷平衡。
上述的优选和实施方案适用于式I。
单齿非离子配体可以例如选自烯烃(例如乙烯、丙烯)、烯丙基类(烯丙基、2-甲代烯丙基)、溶剂化溶剂(腈、直链或环状醚、未烷基化或N-烷基化酰胺和内酰胺、胺、膦、醇、羧酸酯、磺酸酯)、一氧化氮和一氧化碳。
单齿阴离子配体可以例如选自卤离子(F、Cl、Br、I)、假卤离子(氰化物、氰酸根、异氰酸根)和羧酸阴离子、磺酸阴离子和膦酸阴离子(碳酸根、甲酸根、乙酸根、丙酸根、甲磺酸根、三氟甲磺酸根、苯磺酸根、甲苯磺酸根)。
二齿非离子配体可以例如选自直链或环状二烯属烃(例如己二烯、环辛二烯、降冰片二烯)、二腈(丙二腈)、羧酸的未烷基化或N-烷基化二酰胺、二胺、二膦、二醇、乙酰丙酮化物、二羧酸二酯和二磺酸二酯。
二齿阴离子配体可以例如选自二羧酸、二磺酸和二膦酸(例如草酸、丙二酸、琥珀酸、马来酸、亚甲基二磺酸和亚甲基二膦酸)的阴离子。
优选的金属络合物还包括其中E是-Cl-、-Br-、-I-、ClO4 -、CF3SO3 -、CH3SO3 -、HSO4 -、BF4 -、B(苯基)4 -、B(C6F5)4 -、B(3,5-双三氟甲基苯基)4 -、PF6 -、SbCl6 -、AsF6 -或SbF6 -的金属络合物。
适用于氢化的特别优选的金属络合物符合式VI和VII
[A1Me1YZ] (VI), [A1Me1Y]+E1 - (VII),
其中
A1是式I化合物;
Me1是铑和铱;
Y代表两个烯烃或二烯;
Z是Cl、Br或I;且
E1 -是含氧酸或配酸的阴离子。
上述实施方案和优选适用于式I化合物。
当Y是烯烃时,它可以是C2-C12-、优选C2-C6-而特别优选C2-C4-烯烃。实例是丙烯、丁-1-烯和特别是乙烯。二烯可以含有5-12、优选5-8个碳原子,并且可以是开环、环或多环二烯。二烯的两个烯烃基团优选由一个或两个CH2基团连接。实例是1,3-戊二烯、环戊二烯、1,5-己二烯、1,4-环己二烯、1,4-或1,5-庚二烯、1,4-或1,5-环庚二烯、1,4-或1,5-辛二烯、1,4-或1,5-环辛二烯和降冰片二烯。Y优选代表两个乙烯或1,5-己二烯、1,5-环辛二烯或降冰片二烯分子。
在式VI中,Z优选是Cl或Br。E1的实例是ClO4 -、CF3SO3 -、CH3SO3 -、HSO4 -、BF4 -、B(苯基)4 -、PF6 -、SbCl6 -、AsF6 -或SbF6 -。
本发明的钌络合物可以例如符合式VIII
[RuaHbZc(A1)dLe]f(Ek)g(S)h (VIII),
其中
Z是Cl、Br或I;A1是式I化合物;基团L是相同或不同的配体;E-是含氧酸、无机酸或配酸的阴离子;S是能够作为配体配位的溶剂;并且a是1-3,b是0-4,c是0-6,d是1-3,e是0-4,f是1-3,g是1-4,h是0-6且k是1-4,络合物上的净电荷是零。
上述对于Z、A1、L和E-的优选适用于式VIII化合物。另外,配体L还可以是芳烃或杂芳烃(例如苯、萘、甲苯、二甲苯、枯烯、1,3,5-三甲苯、吡啶、联苯、吡咯、苯并咪唑或环戊二烯)和具有路易斯酸功能的金属盐(例如ZnCl2、AlCl3、TiCl4和SnCl4)。溶剂配体可以是例如醇、胺、酰胺、内酰胺和砜。
这种类型的络合物被描述于下面所提到的参考文献和其中引用的
参考文献中:
D.J.Ager,S.A.Laneman,“Tetrahedron:Asymmetry”,8,1997,3327-3355;
T.Ohkuma,R.Noyori in Comprehensive Asymmetric Catalysis(E.N.Jacobsen,A.Pfaltz,H.Yamamoto,Eds.),Springer,Berlin,1999,199-246;
J.M.Brown in Comprehensive Asymmetric Catalysis(E.N.Jacobsen,A.Pfaltz,H.Yamamoto,Eds.),Springer,Berlin,1999,122-182;
T.Ohkuma,M.Kitamura,R.Noyori in Catalytic Asymmetric
Synthesis,2nd Edition(I.Ojima,Ed.),Wiley-VCH New York,2000,1-110;
N.Zanetti等人,Organometallics 15,1996,860。
具有相应的结构式以及其它二膦配体的更具体的钌络合物描述于下列参考文献中:
[RuaHbClc(A1)d芳烃e](胺)h:EP-A1-0269395和EP-A1-0 174 057;
[Rua(A1)]E-,更具体地是[Ru(A1)]E-和[RuH(A1)]E-:EP-A1-0 256 634;
[Ru(A1)(羧酸盐)2]:US-A-4 739 084和AP-A1-0 245 959;
[Ru(A1)2(路易斯酸)](NC2H5)3,[Ru(A1)2(路易斯酸)](乙酸盐):EP-A1-0307 168;
[RuZ(芳烃)(A1)]卤化物,[Ru(Z)(芳烃)(A1)E-:EP-A1-0 366 390
[RuZ2(A1)](手性胺):H.Doucet等人,Angew.Chem.Int.Ed.37,1998,1703;T.Ohkuma等人,J.Am.Chem.Soc.,120,1998 13529;T.Ohkuma等人,J.Am.Chem.Soc.,122,2000,6510.
[RuZ2(A1)](吡啶)2:O.M.Akotsi等人,手性,12(2000)514。
一些具体的和优选的钌络合物是:[Ru(乙酸盐)2(A1)]、[Ru(OOCCF3)2(A1)]、[RuBr2(A1)]、[Rul2(A1)]、[Ru2Cl4(A1)2](Nethyl3)、[Ru2Cl4(A1)2](Nethyl3)(二甲苯)、[RuCl(苯)(A1)]Cl、[RuBr(苯)(A1)]Br、[Rul(苯)(A1)]l、[RuCl(对枯烯)(A1)]Cl、[RuBr(对枯烯)(A1)]Br、[Rul(对-枯烯)(A1)]l、[Ru(2-甲代烯丙基)2(A1)]、[RuCl2(苯基-CN)2(A1)]、[Ru(A1)(AcO)2(乙醇)2]、[(Cp)Ru(A1)]Cl、[(Cp)Ru(A1)]PF6、[RuCl(P苯基3)(A1)]2(η-Cl)2、[RuCl2(A1)(dpen)]和[RuCl2(A1)(daipen)]。Cp是环戊二烯基;dpen和daipen分别是手性乙二胺,例如1,2-二苯基乙-1,2-二胺或1,1-二(对甲氧基苯基)-2-异丙基乙-1,2-二胺。
本发明金属络合物可以通过得自文献的已知方法制备(参见US-A-5,371,256,US-A-5,446,844,US-A-5,583,241和E.Jacobsen,A.Pfaltz,H.Yamamoto(Eds.),“综合性不对称催化I-III”,Springer Vertag,Berlin,1999,和其中引用的参考文献)。
本发明金属络合物是在反应条件下可以被激活、且可以被用于前手性烯键式不饱和有机化合物的不对称氢化的均相催化剂或催化剂前体。这样的使用可溶性均相金属络合物的氢化被描述于例如Pure andAppl.Chem.,Vol.68,No.1,pp.131-138(1996)中。按照本发明,对于氢化优选使用钌、铑和铱。在具有碳双键的前手性化合物的氢化中,可以获得特别好的结果。高活性还能够减少催化剂的量,这就提供了经济上的优越性。
本发明还提供了选自第TM8族金属的金属与包括式I化合物的配体的络合物作为用于通过氢将前手性烯键式不饱和有机化合物氢化的均相催化剂的应用。
本发明的另一个方面是制备手性有机化合物的方法,所述方法是通过在均相催化剂存在下,用氢不对称氢化含有至少一个碳双键的前手性有机化合物,其中氢化是在催化量的至少一种选自第TM8族金属的金属与作为配体的式I化合物的络合物存在下进行的。
优选的被氢化的前手性不饱和化合物可以在开链或环状有机化合物中含有一个或多个相同或不同的基团C=C,其中基团C=C可以是环状系统的部分或者是外向环基团。前手性不饱和化合物可以是烯烃、环烯、杂环烯。它们可以例如符合式IX,
R5R6C=CR7R8 (IX),
其中R5、R6、R7和R8是加以选择的以便化合物是手性的,并且分别彼此独立地是氢或开链或环烃基或含有选自O、S和N的杂原子的杂烃基,所述烃基或杂烃基含有1-30、优选1-20个碳原子;
R5和R6以及它们所键合的碳原子一起形成具有3-12个环原子的烃环或杂烃环;
R5和R7,在每一情况下与它们所键合的C=C基团一起形成具有3-12个环原子的烃环或杂烃环;
杂环中的杂原子选自O、S和N;
并且R5、R6、R7和R8是未被取代的或被下列基团取代:C1-C6烷基、C1-C6烷氧基、环己基、C6-C10芳基、C7-C12芳烷基、C1-C4烷基-C6-C10芳基、C1-C4烷氧基-C6-C10芳基、C1-C4烷基-C7-C12芳烷基、C1-C4烷氧基-C7-C12芳烷基、-OH、-NR11R12、-CO-OR9或-CO-NR10R11,其中R9是H、碱金属、C1-C6烷基、环己基、苯基或苄基,并且R10和R11分别彼此独立地是氢、C1-C6烷基、环己基、苯基或苄基,或者R10和R11一起形成四亚甲基、五亚甲基或3-氧杂亚戊基。
取代基的实例和优选在上面已经提及。
基团R5-R7可以例如是C1-C20烷基、优选C1-C12烷基,C1-C20杂烷基、优选C1-C12杂烷基,所述杂烷基含有选自O、S和N的杂原子,C3-C12环烷基、优选C4-C6环烷基,C-键合的C3-C11杂环烷基、优选C4-C8杂环烷基,所述杂环烷基含有选自O、S和N的杂原子,C3-C12环烷基-C1-C6烷基、优选C4-C8环烷基-C1-C6烷基,C3-C11杂环烷基-C1-C6烷基、优选C4-C8杂环烷基-C1-C6烷基,所述杂环烷基含有选自O、S和N的杂原子,C6-C14芳基、优选C6-C10芳基,C5-C13杂芳基、优选C5-C9杂芳基,所述杂芳基含有选自O、S和N的杂原子,C7-C15芳烷基、优选C7-C11芳烷基,C6-C12杂芳烷基、优选C6-C10杂芳烷基,所述杂芳烷基含有选自O、S和N的杂原子。
当R5和R6或R5和R7在每一情况下与它们所键合的基团一起形成烃环或杂烃环时,所述环优选含有4-8个环原子。杂烃环可以例如含有1-3、优选1或2个杂原子。
不饱和有机化合物的一些实例是不饱和羧酸和二羧酸、酯、酰胺和盐,例如α-和可能β-取代的丙烯酸或巴豆酸。优选的羧酸是式
R12-CH=C(R13)-C(O)OH
的羧酸和它们的盐、酯和酰胺,其中R12是C1-C6烷基,未取代的C3-C8环烷基或被1-4个C1-C6烷基、C1-C6烷氧基或C1-C6烷氧基-C1-C4烷氧基取代的C3-C8环烷基,或者未取代的C6-C10芳基或被1-4个C1-C6烷基、C1-C6烷氧基或C1-C6烷氧基-C1-C4烷氧基取代的C6-C10芳基,优选苯基,并且R13是直链或支链C1-C6烷基(例如异丙基),未取代的或取代的(以上面所定义的方式)环戊基、环己基、苯基或被保护的氨基(例如乙酰基氨基)。用于氢化的更为具体的底物是例如前手性烯丙醇和α-或β-烯酰胺。
本发明方法可以在低温或高温条件下进行,例如在-20-150℃、优选-10-100℃、特别优选10-80℃温度下进行。通常低温条件下的旋光产率高于高温条件下的旋光产率。
本发明方法可以在大气压下或超大气压下进行。压力可以是例如104-2×107Pa(帕斯卡),优选105-2×106Pa,特别优选为大气压-106Pa。
优选将催化剂以0.00001-10mol%、特别优选0.0001-10mol%、特别是0.001-5mol%的量使用,所述百分比是基于被氢化的化合物计的。被氢化的化合物与均相催化剂的摩尔比可以是例如10-10000000,更优选20-100000。
催化剂的制备以及氢化和加成反应可以在存在或不存在惰性溶剂的条件下进行,并且可以使用一种溶剂或溶剂的混合物。适宜的溶剂是例如脂族、环脂族和芳族烃(戊烷、己烷、庚烷、石油醚、环己烷、甲基环己烷、苯、甲苯、二甲苯),脂族卤代烃(二氯甲烷、氯仿、二氯乙烷和四氯乙烷),腈(乙腈、丙腈、苄腈),醚(乙醚、二丁基醚、叔丁基甲基醚、乙二醇二甲醚、乙二醇二乙醚、二甘醇二甲醚、四氢呋喃、二恶烷、二甘醇一甲醚或一乙醚),酮(丙酮、甲基异丁基酮),羧酸酯和内酯(乙酸乙酯或乙酸甲酯、戊内酯),N-取代的内酰胺(N-甲基吡咯烷酮),酰胺类(二甲基乙酰胺、二甲基甲酰胺),无环脲(二甲基咪唑啉)和亚砜和砜(二甲亚砜、二甲基砜、四亚甲基亚砜、环丁砜)和醇(甲醇、乙醇、丙醇、丁醇、乙二醇一甲醚、乙二醇一乙醚、二甘醇一甲醚),硝基甲烷和水。
反应可以在助催化剂例如季铵卤化物(碘化四丁铵)存在下,和/或在质子酸例如无机酸(参见例如US-A-5,371,256,US-A-5,446,844和US-A-5,583,241和EP-A-0 691 949)存在下进行。助催化剂对于氢化是特别有用的。
可以将用作催化剂的金属络合物作为单独制备的隔离的化合物添加,或者在反应前原位形成然后与被氢化的底物混合。在使用隔离的金属络合物的反应中额外添加配体,或者在原位制备中使用过量配体是有利的。所述过量可以是例如1-30mol%,优选1-10mol%,所述百分比是基于用于制备的金属化合物计的。在催化剂的原位制备,也可以使用二膦配体的盐,例如卤化物或四氟硼酸盐。
本发明方法通常是这样进行的:首先将催化剂放置于反应容器中,然后加入底物或者反之亦然,如果适当的话加入反应助剂,然后加入氢,之后开始反应。优选将氢在压力下导入。该方法可以在各种类型反应器中连续或分批进行。
可以按照本发明制备的手性有机化合物是活性物质,或者是制备这样物质的中间体,这在药物和农药的制备领域中尤其如此。
下面实施例对本发明予以例证说明。
A)制备二膦
实施例A1:制备(αR,αR)-2,2′-双(α-N,N-二甲基氨基苯基甲基)-(S,S)-1,1′-双[二(3,5-二甲基-4-甲氧基苯基)膦基]二茂铁
按照下列文献中描述的方法制备(R,R)-1,1′-双(α-N,N-二甲基氨基苯基甲基)二茂铁:a)J.J.Almena Perea,A.Borner,P.Knochel,“四面体Lett.”1998,39(44),8073-8076;b)J.J.Almena Perea,M.Lotz,P.Knochel,“Tetrahedron:Asymmetry”1999,10(2),375-384;c)L.Schwink,P.Knochel,“Tetrahedron Lett.1996,37(1),25-28.d)L.Schwink,P.Knochel,Chem.Eur.J.,1998,4(5),950-968)。在0℃于氩气氛下,用5分钟时间将叔丁基锂(4.42ml,6.63mmol,3.0当量;1.5M在戊烷中的溶液)滴加到(R,R)-1,1′-双(α-N,N-二甲基氨基苯基甲基)二茂铁(1.00g,2.21mmol)在无水叔丁基甲基醚(TBME)(20ml)中的溶液中。把获得的溶液在0℃搅拌1小时。随后用5分钟时间加入氯化双(3,5-二甲基-4-甲氧基苯基)-膦(2.61g,7.74mmol,3.5当量),并在室温将反应混合物搅拌1小时。把混合物倒入饱和NaHCO3溶液(100ml)中,分离出有机相并将水相用TBME(3×100ml)萃取。把合并的有机相用饱和NaCl溶液(100ml)洗涤,用Na2SO4干燥,过滤并在旋转蒸发仪上除去溶剂。将粗产物溶解于CH2Cl2中,并用柱色谱法纯化(250g硅胶,正庚烷/TBME 2∶1);Rf(正庚烷/TBME 2∶1):0.11)。把所得黄色固体(1.10g)悬浮于甲醇(5ml)中并回流15分钟。冷却至室温后,将悬浮液过滤,并将以此方式获得的固体干燥。获得黄色固体形式的本标题化合物(0.73g,0.69mmol,产率为31%)。31P-NMR(C6D6):-22.7ppm(s);旋光性[a]D 20:-61.5°(C=1.0,CHCl3)。
实施例A2:制备(αR,αR)-2,2′-双(α-N,N-二甲基氨基苯基甲基)-(S,S)-1,1′-双[二(3,5-二甲基苯基)膦基]二茂铁
在0℃于氩气氛下把20g(44.2mmol)(R,R)-1,1′-双(α-N,N-二甲基氨基苯基甲基)二茂铁与160ml TBME一起置于反应器中。然后在0-3℃用40分钟时间滴加88.4ml叔丁基锂(1.5M在戊烷中的溶液,132.6mmol)。将反应溶液在0℃再搅拌2小时。随后在3-7℃滴加42.82g(154.7mmol)双(3,5-二甲基苯基)氯膦在100ml TBME中的悬浮液。将该反应溶液先是在0℃搅拌2小时,然后在室温搅拌过夜。
然后将该溶液在0℃用250ml饱和碳酸氢钠水溶液水解,并将混合物用TBME萃取。将有机相用饱和氯化钠溶液洗涤,合并,用硫酸钠干燥,过滤然后蒸发至干。
如此得到62g粗产物。在硅胶60上色谱纯化两次,用己烷/乙酸乙酯19∶1(然后转换成己烷/乙酸乙酯9∶1)洗脱,得到12.9g(44.2mmol;31%)本标题化合物。从乙醚/戊烷中重结晶,得到6.56g(7.03mmol;15.9%)分析纯的(αR,αR)-2,2′-双(α-N,N-二甲基氨基苯基甲基)-(S,S)-1,1′-双[二(3,5-二甲基苯基)膦基]二茂铁。
B)应用实施例
实施例B1:制备甲基N-乙酰基苯基丙氨酸
通过重复抽真空和吹洗,在氩气氛下将4.7mg(0.0126mmol)[Rh(降冰片二烯)2]BF4和13.9mg(0.0132mmol)得自实施例A1的化合物置于配备有磁搅拌器的烧瓶中。加入5ml脱气甲醇后,把溶液搅拌15分钟。随后将2.77g(0.01265mol)顺式-乙酰氨基肉桂酸甲酯和5ml脱气甲醇依次导入充满氩气的10ml Schlenk烧瓶中,并搅拌15分钟。底物/催化剂的比例是1000。用钢毛细管将催化剂溶液和底物溶液依次注入充满氩气的100ml玻璃反应器中。最后,在4个吹洗循环(氩气/氢气)中引入1.05巴氢气。将玻璃反应器加热至25℃,接通搅拌器来开始氢化。通过氢气的消耗(氢气贮器中的压力降低)来监测反应进程。反应2小时后,测定产物的转化率和对映体纯度(用GC:柱Chirasil-L-Val 50m)。转化率为100%,对映体选择性(ee)为98.7%(R)。
实施例B1的比较
重复实施例B1的过程,但是使用配体(αR,αR)-2,2′-双(α-N,N-二甲基氨基苯基甲基)-(S,S)-1,1′-双(二苯膦基)二茂铁(10.8mg,0.0132mmol)。直到4小时后才完成反应。转化率为100%,甲基N-乙酰基苯基丙氨酸的对映体纯度(ee)为97.6%(R)。
实施例B2:制备甲基N-乙酰基苯基丙氨酸
用与实施例B1类似的方法进行制备。使用6.9g(31.48mmol)顺式-乙酰氨基肉桂酸甲酯、1.2mg(0.0032mmol)[Rh(降冰片二烯)2]BF4、3.7mg(0.0035mmol)得自实施例A1的化合物和总共40ml甲醇。底物/催化剂的比例为10000。反应温度为35℃,氢的压力为1.05巴。1.3小时后,停止反应。转化率为100%,甲基N-乙酰基苯基丙氨酸的对映体纯度(ee)为98.6%(R)。
实施例B3:制备甲基N-乙酰基苯基丙氨酸
用与实施例B1类似的方法进行制备。使用13.8g(63.01mmol)顺式-乙酰氨基肉桂酸甲酯、1.2mg(0.0032mmol)[Rh(降冰片二烯)2]BF4、3.7mg(0.0035mmol)得自实施例A1的化合物和总共80ml的甲醇。底物/催化剂的比例为19640。反应温度为25℃,氢气的压力为1.05巴。7小时后,停止反应。转化率为100%,甲基N-乙酰基苯基丙氨酸的对映体纯度(ee)为98.6%(R).
实施例B4:制备2-甲基丁酸
通过重复抽真空和吹洗,在氩气氛下把6.2mg(0.0063mmol)[Rul2(枯烯)]2和得自实施例A1的14.0mg(0.0133mmol)(αR,αR)-2,2′-双(α-N,N-二甲基氨基苯基甲基)-(S,S)-1,1′-双[二(3,5-二甲基-4-甲氧基苯基)膦基]二茂铁置于配备有磁搅拌器的烧瓶中。加入5ml脱气甲醇后,把溶液搅拌15分钟。随后将0.253g(2.53mol)巴豆酸和5ml脱气甲醇依次导入充满氩气的10ml Schlenk烧瓶中并搅拌15分钟。底物/催化剂的比例为200。用钢毛细管将催化剂溶液和底物溶液依次注入充满氩气的50ml高压釜中。最后,最后,在4个吹洗循环(氩气/氢气)中引入1.05巴氢气。将高压釜加热至25℃,接通搅拌器来开始氢化。通过氢气的消耗(氢气贮器中的压力降低)来监测反应进程。反应18小时后,测定产物的转化率和对映体纯度(用GC:柱Betadex 110,30m)。转化率为100%,对映体选择性(ee)为97.2%。
实施例B5:制备甲基N-乙酰基苯基丙氨酸
重复实施例B1的过程,使用555mg(2.53mmol)乙酰氨基肉桂酸甲酯。底物/催化剂的比例为100。将得自实施例A2的(αR,αR)-2,2′-双(α-N,N-二甲基氨基苯基甲基)-(S,S)-1,1′-双[二(3,5-二甲苯基)膦基]二茂铁用作配体。1小时后转化率为100%;ee=98.7%。
Claims (14)
2. 权利要求1的化合物,其中在式I化合物中R1是苯基。
3. 权利要求1的化合物,其中所述开链仲氨基R2符合式R5R6N-,其中R5和R6分别彼此独立地是C1-C6烷基、C3-C8环烷基、C6-C10芳基或C7-C11芳烷基,其中所述环烷基和芳基是未取代的或被C1-C4烷基或C1-C4烷氧基取代,或者R5与R6一起形成四亚甲基、五亚甲基或3-氧杂亚戊基。
4. 权利要求3的化合物,其中R5和R6分别是甲基。
5. 权利要求1的化合物,其中两个基团R3都是甲基、叔丁基或甲氧基。
6. 权利要求1的化合物,其中R4是H或甲氧基。
7. 权利要求1的化合物,其中,在式I化合物中,R1是苯基,R2是二-C1-C4烷基氨基,R3是甲基、叔丁基或甲氧基,并且R4是H、甲基或甲氧基。
8. 权利要求7的化合物,其中所述R2是二甲基氨基。
9. 选自Cu、Ag、Au、Ni、Co、Rh、Pd、Ir、Ru和Pt的金属与作为配体的权利要求1的式I化合物的络合物。
10. 权利要求9的金属络合物,其中所述金属是铑、铱或钌。
11. 权利要求9的金属络合物,所述金属络合物符合式IV和V,
A1MeLn (IV), (A1MeLn)(Z+)(E-)z (V),
其中A1是权利要求1的式I化合物,
基团L是相同或不同的单齿阴离子或非离子配体,或者基团L是相同或不同的二齿阴离子或非离子配体;
当L是单齿配体时n是2、3或4,或者当L是二齿配体时n是1或2;
z是1、2或3;
Me是选自Rh和Ir的金属;所述金属具有氧化态0、1、2、3或4;
E-是含氧酸或配酸的阴离子;并且
阴离子配体与金属的氧化态1、2、3或4的电荷平衡。
12. 权利要求9的金属络合物,所述金属络合物是式VIII的钌络合物
[RuaHbZc(A1)dLe]f(Ek)g(S)h (VIII),
其中
Z是Cl、Br或I;A1是权利要求1的式I化合物;基团L是相同或不同的配体;E-是含氧酸、无机酸或配酸的阴离子;S是能够作为配体配位的溶剂;并且a是1-3,b是0-4,c是0-6,d是1-3,e是0-4,f是1-3,g是1-4,h是0-6,且k是1-4,其中a至k中各个都为整数,络合物上的净电荷是零。
13. 制备手性有机化合物的方法,所述方法是通过在均相催化剂存在下,用氢不对称氢化含有至少一个碳双键的前手性有机化合物,其中氢化是在催化量的至少一种选自Cu、Ag、Au、Ni、Co、Rh、Pd、Ir、Ru和Pt的金属与作为配体的权利要求1的式I化合物的络合物存在下进行的。
14. 选自Cu、Ag、Au、Ni、Co、Rh、Pd、Ir、Ru和Pt的金属与作为配体的权利要求1的式I化合物的络合物作为用于通过氢不对称氢化前手性烯键式不饱和有机化合物的均相催化剂的应用。
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US8507705B2 (en) * | 2006-06-08 | 2013-08-13 | Shanghai Jiaotong University | C2-symmetrical ruthenocene diphosphine ligands only with surface chirality and their manufacture |
JP5126626B2 (ja) | 2007-02-01 | 2013-01-23 | インターベツト・インターナシヨナル・ベー・ベー | 6−アミノ−7−ヒドロキシ−4,5,6,7−テトラヒドロ−イミダゾ[4,5,1−jk][1]−ベンゾアゼピン−2[1h]−オンおよびジルパテロールのエナンチオ選択的合成 |
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