CN1301267A - 光学活性膦烷的生产 - Google Patents

光学活性膦烷的生产 Download PDF

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CN1301267A
CN1301267A CN99806300A CN99806300A CN1301267A CN 1301267 A CN1301267 A CN 1301267A CN 99806300 A CN99806300 A CN 99806300A CN 99806300 A CN99806300 A CN 99806300A CN 1301267 A CN1301267 A CN 1301267A
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R·斯蒂尔斯
A·贝纳
J·霍尔兹
G·沃斯
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Abstract

本发明涉及通式(I)的膦烷及二膦烷,其中:R代表氢、C1～C6—烷基、芳基、烷芳基、SiR3 2;R2代表烷基或芳基;A代表氢、C1～C6—烷基、芳基、C1或者(a);以及B代表2个磷原子之间的1～5个碳原子的连接基。本发明还涉及所述膦烷及二膦烷作为催化剂在不对称合成中的应用。

Description

光学活性膦烷的生产
本发明描述新型光学活性膦烷(phospholane)及双磷烷，其制备及其作为金属络合物中配位体的应用，以及该金属络合物在对映体选择性合成中的应用。
涉及铑及钌络合物的对映体选择性氢化及异构化，在光学活性化合物的合成中占有非常重要的地位(例如参见，Tani等人，《美国化学学会会报》106,5211,1984；R.Noyori，《美国化学研究报告》23,345(1990))。化学计量的原料氢虽然花费很少，但是所采用的催化剂，大多由光学活性二膦配位体及铑或钌化合物制备，却成本非常高，且只能通过复杂方式制取。
光学活性膦及二膦的已知制备方法全都很复杂并且一般都包括技术上繁杂、成本高昂的外消旋拆分(例如，EP-A0614901、EP-A0271311；H.B.Kagan，“不对称催化中的手性配位体”，《不对称合成》，卷5(1985),pp.13～23；EP-A0151282、EP-A 0185882；R.Noyori，《美国化学研究报告》23,345(1990)；EP-269395；M.J.Burk,《四面体.不对称》，pp.569～592(1991)；《美国化学学会会报》113,pp.8518-9(1991)；同一出处，115,pp.10125～138(1993)；同处，117,pp.9375～76(1995)；同处，118,pp.5142(1996))。这些缺陷使其在工业应用起来困难而且不经济。
本发明的目的是提供一种膦配位体，它容易制备且成本低，而且是对映体选择性合成金属络合物催化剂用的优良配位体。
我们发现，这一目的可由一类特别高效的配位体，主要是膦烷，来实现，这类配位体可由其“手性资源”获得。这种情况下的原料是甘露糖醇以及其他可低成本地大量制取的碳水化合物。
生成的膦烷及二膦烷可在不对称氢化中提供极好的对映体过量。Burk等人的已知DUPHOS配位体(M.J.Burk，《四面体·不对称》，pp.569～592(1991)；《美国化学学会会报》113,pp.8518-9(1991)；同一出处，115,pp.10125～138(1993)；同处，117,pp.9375～76(1995)；同处，118,pp.5142(1996)；US5,008,457、WO92/19630、WO93/19040)，与本发明相比，合成起来非常繁琐。DUPHOS配位体的合成，除了不对称氢化之外还要求，尤其是难以实现的电解Kolbe(科尔伯)合成。
本发明由于采用天然来源对映体纯级的糖类甘露糖醇，故避免了这些困难。另外，这种前体还可为获得在膦烷环的2和5位上具有烷氧甲基或羟甲基基团的化合物提供途径。这种类型的化合物无法通过已知的DUPHOS合成来制备。
本发明涉及通式Ⅰ的膦烷及二膦烷，
Figure A9980630000051
其中：
R是氢、C1～C6-烷基、芳基、烷芳基，SiR3 2,
R2是烷基或芳基，
A是氢、C1～C6-烷基、芳基、Cl或
Figure A9980630000052
B是2个磷原子之间的1～5个碳原子的连接基。
优选的取代基R是氢、甲基、乙基、正丙基、异丙基、正丁基、异丁基、叔丁基、苄基、trityl及三烷基甲硅烷基或三芳基甲硅烷基
(SiR3 2，其中R2=C1～C6-烷基或芳基)。
在二膦烷的情况下，优选的那些具有其中n=0,1,2,3,4或
Figure A9980630000062
其中m=0,1,2,3
R3=烷基或稠合芳基
尤其优选的连接基B是结构式中n等于1或2且m是0的那些。
本发明还涉及包含上述膦烷的金属络合物，其中中心原子选自Rh、Ru、Ir、Pd、Pt、Ni。
尤其优选的金属络合物是包含钌或铑作为中心原子的那些。
这些络合物可这样来制备，即，按已知方法(例如，Uson，《无机化学学报》73,275(1983)；EP-A 0158875、EP-A 437690)通过与包含易变配位体的铑、铱、钌、钯、铂或镍络合物(例如，{RuCl2(COD)]n、Rh(COD)2BF4、Rh(COD)2ClO4、[Ir(COD)Cl]2、氯化对散花-钌二聚体)之间的反应来合成该催化活性络合物。
本发明还涉及这些金属络合物在不对称合成中的应用，尤其是作为氢化、加氢甲酰基化、氢氰化、烯丙基取代以及由烯丙基胺到烯胺的异构化等的催化剂。
这类反应可借助本发明的金属络合物在本领域技术人员熟悉的条件下进行。
借助本发明金属络合物的氢化通常在-20～150℃，优选0～100℃，尤其优选15～40℃的温度进行。
按照本发明的氢化方法的氢气压力可在0.1bar～300bar的宽范围变化。非常好的结果可在1～10，优选1～2bar范围的压力下获得。
采用本发明配位体尤其有利之处在于，  氢化可在1～2bar氢气低压力下非常高效地实施。
优选的氢化溶剂是C1～C4-链烷醇，尤其是甲醇。在被作用物溶解度低的情况下，溶剂混合物如甲醇与CH2Cl2，或THF、甲苯等也是合适的。
催化剂的用量，以待氢化被作用物为基准，一般介于0.001～5mol％，优选0.001～0.01mol％。
实例1实验部分
Figure A9980630000071
Figure A9980630000081
1,2；5,6-二-O-异丙叉-3,4-O-硫代羰基-D-甘露糖醇(1)：
采用E.J.Corey等人的方法1，使1,2；5,6-二-O-异丙叉-D-甘露糖醇与硫光气在4-二甲氨基吡啶存在下、在二氯甲烷中进行反应，收率为90％。
E-3,4-二脱氢-3,4-二脱氧-1,2；5,6-二-O-异丙叉-D-苏-己糖醇(2)：
环状硫代碳酸酯1，按文献2,3在亚磷酸三乙酯中加热20h，生成反式-烯烃，收率为80～90％。
3,4-二脱氧-1,2；5,6-二-O-异丙叉-D-苏-己糖醇(3)：
按Machinaga等人方法4的改良方法，烯烃2(10g)在甲醇中、10％活性炭载铂(250mg)的存在、大气压压力下氢化生成化合物3。经柱色谱术提纯后，收率为80～90％。化合物3还可按照文献4通过蒸馏进行提纯(沸点0.6mm=73℃)。
3,4-二脱氧-D-苏-己糖醇(4)：
按照文献4，异丙叉基团在1N盐酸中发生酸解。生成的化合物经过重结晶以后获得的收率为85％。
(2S,5S)-1,6-双(苄氧基)-2,5-己二醇(5)：
3.0g(20mmol)3,4-二脱氧-D-苏-己糖醇(4)按Marzi等人的方法5，转化为3.70g 1,6-二-O-苄基化产物5，收率为56％。
(2S,5S)-1,6-双[(叔丁基二苯基甲硅烷基)氧基]-2,5-己二醇(6)：
3.0g(20mmol)化合物4与叔丁基二苯基氯硅烷在DMF中、咪唑存在下按文献5起反应生成衍生物6，收率为80％。
(4S,7S)-4,7-双(苄氧基甲基)-2,2-二氧代[1,3,2]-dioxo-thiepane(7)：
1.43g(12mmol)亚硫酰氯在氩气氛下缓慢地加入到3.30g(10mmol)二醇5在70mL干燥四氯甲烷中的体系中，  然后混合物回流90min。在旋转蒸发器中赶出溶剂以后，残余物溶解在四氯甲烷(40mL)、乙腈(40mL)及水(60mL)的混合物中，然后在0℃下，加入15mg(72μmol)RuCl3*3H2O及4.28g(20mmol)高碘酸钠。然后混合物在室温搅拌1h，继而在悬浮体中加入50mL水。随后以二乙醚(3×75mL)萃取并以饱和氯化钠溶液(100mL)洗涤有机相，然后干燥(硫酸钠)，形成的残渣经过柱色谱术处理(正已烷∶乙酸乙酯=2∶1,Rf=0.20)给出化合物7，收率3.37g(86％)。
熔点=57to 59℃；[α]D 26=-37.2°(c1.01；CHCl3)；1H-NMR(CDCl3,400MHz)δ7.34(10H,m,arom.H),4.78(2H,m,H-2/5),4.57(2H,AB-sp.,Ha-CH2Ph,2Ja,b=12.0Hz),4.56(2H,AB-sp.,Hb-CH2Ph,2Ja,b=12.0Hz),3.65(2H,dd,Ha-CH2OH,2Ja,b=10.8Hz,3JH,H=5.4Hz),3.56(2H,dd,Hb-CH2OH,2Ja,b=10.8Hz,3JH,H=4.9Hz),2.00(4H,m,H-3/4)；13C-NMR(CDCl3,100MHz)δ137.3,128.4-127.7(arom.C),82.6(C-2/5),73.4(CH2Ph),70.8(C-1/6),28.9(C-3/4)；元素分析C20H24O6S(392.47)计算值：C61.21,H6.16,S8.17；测定值：C61.03,H6.19,S8.10；
1,6-二-O-(叔丁基二苯基)甲硅烷基-2,5-O-异丙叉-3,4-二脱氧-D-苏-己糖醇(8)：
6.27g(10mmol)化合物6按文献5转化为异丙叉衍生物8，收率85％(5.67g)。8用柱色谱术提纯(正己烷∶二乙醚=19∶1,Rf=0.2)，以便鉴定。若用于下一步反应，  则该化合物不需要提纯。
2,5-O-异丙叉-3,4-二脱氧-D-苏-己糖醇(9)：
6.67g(10mmol)甲硅烷基化合物8借助氟化四丁铵溶于THF的溶液脱除甲硅烷基基团5，随后色谱提纯(二乙醚∶甲醇=19∶1,Rf=0.5)，生成1.7g(89％)二醇9。
2,5-O-异丙叉-1,6-二-O-甲基-3,4-二脱氧-D-苏-己糖醇(10)：
3.80g(20mmol)二醇9溶于30mL THF的溶液在0℃加入到1.06g(44mmol)NaH溶于60mL THF的溶液中。醇盐生成反应完成之后，慢慢加入2.2当量碘甲烷(6.21g,44mmol)，混合物在室温搅拌。反应完成之后，以水(30mL)小心地将过量NaH分解，然后在减压下赶出THF。然后，以二氯甲烷(3×50毫升)萃取剩余水溶液，干燥(硫酸钠)合并的有机相。浓缩后获得的残渣经柱色谱术(正己烷∶乙酸乙酯=2∶1,Rf=0.40)获得无色糖浆，收率84％(3.68g)。糖浆；[α]D 23=-32.8°(c1.01,CHCl3)；1H-NMR(CDCl3,400MHz)δ3.92(2H,m,H-2/5),3.32(2H,dd,Ha-CH2O,2Ja,b=9.9Hz,3JH,H=6.3Hz),3.30(6H,s,CH3),3.55(2H,m,Hb-CH2O,2Ja,b=9.9Hz,3JH,H=5.3Hz),1.67(2H,m,Ha-3/4),1.34(2H,m,Hb-3/4),1.31(6H,s,CH3)；13C-NMR(CDCl3,100MHz)δ100.5(C(O)2),76.2(C-1/6),70.4(C-2/5),59.1(CH3),31.1(C-3/4),25.6(C(CH3)2)；
元素分析C11H22O4(218.293)计算值：C60.52,H10.16；测定值：C60.38,H10.07；
(2S,5S)-1,6-双(苄氧基)-2,5-己二醇(11)：
4.0g(18.32mmol)化合物10在60mL THF与60mL 1N盐酸混合物中水解20min。溶液在旋转蒸发器中浓缩之后，经色谱术(乙醇∶乙酸乙酯=1∶3,Rf=0.45)处理生成3.20g浅黄色糖浆11，收率几乎达到定量水平。糖浆；[α]D 22=-7.2°(c1.09,CH3OH)；1H-NMR(CD3OD,400MHz)δ3.72(2H,m,H-2/5),3.37(6H,s,CH3),3.38-3.30(4H,m,CH2OH),1.56(4H,m,H-3/4)；13C-NMR(CD3OD,100MHz)δ78.2(C-1/6),70.1(C-2/5),59.2(CH3),30.6(C-3/4)；元素分析C8H18O4(178.228)计算值：C53.91,H10.18；测定值：C53.47,H10.14；
(4S,7S)-4,7-双(甲氧基甲基)-2,2-二氧代[1,3,2]-dioxo-thiepane(12)：
1.78g(10mmol)二醇11按类似于环状硫酸酯7的制备转化为目标化合物12。这种情况下，也可不实施色谱术(正己烷∶乙酸乙酯=1∶2,Rf=0.4)的提纯步骤，因为，产物12可通过结晶从二乙醚/正己烷中以白色固体形式分离出来，收率76％(1.83g)。
熔点=75-78℃；[α]D 23=-44.1°(c1.01；CHCl3)；1H-NMR(CDCl3,400MHz)δ4.72(2H,m,H-2/5),3.56(2H,dd,Ha-CH2O,2Ja,b=10.8Hz,3JH,H=5.4Hz),3.47(2H,dd,Ha-CH2O,2Ja,b=10.8Hz,3JH,H=4.7Hz),3.37(6H,s,CH3),2.04-1.92(4H,m,H-3/4)；13C-NMR(CDCl3,100MHz)δ82.5(C-2/5),73.4(C-1/6),59.3(OCH3),28.8(C-3/4)；元素分析C8H16O6S(240.274)计算值：C39.99,H6.71,S13.34；测定值：C40.06,H6.76,S1.27；
1,2-双[(2R,5R)-2,5-苄氧基甲基膦烷基(phospholanyl)]苯(13)：
2.0当量正丁基锂(4.58mL,1.6M正己烷中的溶液)慢慢加入到0.52g(3.66mmol)1,2-双(氧膦基)-苯溶于50mL THF的溶液中，2h后，在所形成的黄色溶液中慢慢加入2.86g(7.32mmol)环状硫酸酯7溶于20mL THF的溶液。混合物在室温再搅拌2h，最后，再次加入2.2当量正丁基锂(5.03mL,1.6M溶于正己烷的溶液)。溶液搅拌过夜，最后以2mL甲醇破坏多余的正丁基锂。减压下赶出溶剂，残余物在绝氧条件下溶于20mL水中并以二氯甲烷萃取(2×50mL)。有机相干燥(硫酸钠)后，赶出溶剂。利用柱色谱术(正己烷∶乙酸乙酯=4∶1,Rf=0.35)分离出要求的产物，获得0.52g(19％)浅黄色糖浆。糖浆；1H-NMR(CDCl3,400MHz)δ7.45-7.10(24H,m,arom,H),4.49(2H,AB-sp.,Ha-CH2Ph,2Ja,b=12.1Hz),4.47(2H,AB-sp.,Hb-CH2Ph,2Ja,b=12.1Hz),4.18(2H,AB-sp.,Ha-CH2Ph,2Ja,b=11.9Hz),4.04(2H,AB-sp.,Hb-CH2Ph,2Ja,b=11.9Hz),3.65-3.45(4H,m,CH2O),2.97-2.80(4H,m,CH2O),2.70(2H,m,CH-P)；2.33(4H,m,CH-P,Ha-(CH2)2)；2.18(2H,m,Ha-(CH2)2),1.80-1.53(4H,m,Hb-(CH2)2)；13C-NMR(CDCl3,100MHz)δ141.8(m,Car-P),138.6+138.5(ipso-C),131.8,128.4-127.1(arom.C),74.1(m,CH2Ph),73.0(CH2Ph),72.5(CH2O),72.5(CH2O),39.5(CH-P),38.9(m,CH-P),30.9(CH2),30.4(CH2)；31P-NMR(CDCl3,162MHz)δ11.5；
1,2-双[(2R,5R)-2,5-甲氧基甲基膦烷基]苯(14)：
按类似于双磷烷13的制备，以化合物12替代环状硫酸酯7起反应，生成要求的甲氧基甲基-取代的双膦烷14。按柱色谱术进行提纯和分离(正己烷∶乙酸乙酯=2∶1,Rf=0.20)，获得0.80g(48％)无色糖浆。糖浆；1H-NMR(CDCl3,400MHz)δ7.45(2H,m,arom.H),7.30(2H,m,atom.H),3.55(4H,m,CH2O),3.36(2H,m,CH2O),3.35(6H,s,CH3),3.10(6H,s,CH3),2.90(2H,m,CH2O),2.78(2H,m,CH-P),2.63(2H,m,CH-P),2.32(2H,m,CH2)；2.16(4H,m,CH2)；1.68(2H,m,CH2),1.55(4H,m,CH2)；13C-NMR(CDCl3,100MHz)δ141.9(m,Car-P),131.8,128.4(arom.C),74.1(m,CH2Ph),76.6(m,CH2O),74.5(CH2O),58.8(CH3),58.2(CH3),39.6(CH-P),39.0(m,CH-P),30.9(CH2),30.3(CH2)；31P-NMR(CDCl3,162MHz)δ-11.7；
1,2-双[(2R,5R)-2,5-苄氧基甲基膦烷基]乙烷·硼烷络合物(15)：
7.40mmol(4.63mL)1.6M正丁基锂／己烷溶液，在室温下加入到348mg(3.70mmol)双(氧膦基)乙烷/THF溶液中。混合物搅拌2h。然后，慢慢加入2.90g(7.40mmol)环状硫酸酯7溶于20mL THF的溶液，混合物再搅拌2h。随后，再加入5.09mL(8.14mmol)正丁基锂溶液，搅拌过夜后反应便告完成。为生成硼烷加成产物，溶液冷却至-20℃，然后加入9.25mL(9.25mmol)1M BH3/THF溶液。2h后，加入2mL甲醇以破坏多余丁基锂及BH3，减压下赶出溶剂。残余物溶解在水中，然后以二氯甲烷萃取。随后，萃取液进行干燥(硫酸钠)并浓缩，残余物通过柱色谱术(正己烷∶乙酸乙酯=4∶1,Rf=0.20)提纯。获得350mg(13％)粘稠糖浆。糖浆；1H-NMR(CDCl3,400MHz)δ7.37-7.22(20H,m,arom.H),4.47(2H,AB-sp.,Ha-CH2Ph,2Ja,b=11.2Hz),4.42(2H,AB-sp.,Ha-CH2Ph,2Ja,b=12.1Hz),4.41(2H,AB-sD.,Hb-CH2Ph,2Ja,b=12.1Hz),4.38(2H,AB-sp.,Hb-CH2Ph,2Ja,b=11.2Hz),3.58(4H,m,CH2O),3.43(4H,m,CH2O),2.37(2H,m,CH-P)；2.14-1.79(10H,m,CH-P,(CH2)2),1.41-1.20(2H,m,(CH2)2),0.85-0.00(6H,m,BH3)；13C-NMR(CDCl3,100MHz)δ138.1+137.9(ipso-C),128.3-127.4(arom.C),73.2(CH2Ph),72.7(CH2Ph),69.4(CH2O),68.4(CH2O),39.5(m,CH-P),29.1(CH2),28.6(CH2),15.9(m,CH2)2)；31P-NMR(CDCl3,162MHz)δ40.2；
1,2-双[(2R,5R)-2,5-甲氧基甲基膦烷基]乙烷·硼烷络合物(16)：
2.14g(8.91mmol)环状硫酸酯12与0.42g(4.45mmol)双(氧膦基)乙烷按类似于化合物15的制备起反应生成要求的硼烷保护的双膦烷16。以色谱术提纯，其中正己烷∶乙酸乙酯=2∶1(Rf=0.15)。获得结晶产物，收率0.71g(39％)。
熔点=45-48℃；[α]D 23=21.9°(c1.00；CHCl3)；1H-NMR(CDCl3,400MHz)δ3.51(8H,m,CH2O),3.33(6H,s,CH3O),3.32(6H,m,CH3O),2.36(2H,m,CH-P)；2.23-2.05(6H,m,CH-P,(CH2)2),1.96(4H,m,CH2)2),1.58-1.35(4H,m,(CH2)2),0.95-0.00(6H,m,BH3)；13C-NMR(CDCl3,100MHz)δ71.6(m,CH2O),70.8(CH2O),58.7(CH3O),58.7(CH3O),39.5(m,CH-P),29.1(CH2),28.9(CH2),15.8(m,CH2)2)；31P-NMR(CDCl3,162MHz):δ40.5；MS(m/z；EI)391[M+-BH4](100)；
1,2-双[(2R,5R)-2,5-甲氧基甲基膦烷基]乙烷(17)：
0.30g(0.42mmol)硼烷络合物15在40℃与0.142g(1.26mmol)DABCO溶于6mL甲苯的绝氧溶液进行混合。反应完成之后，溶液浓缩并经过快速柱色谱术(正己烷∶乙酸乙酯=4∶1,Rf=0.55)提纯。获得双膦烷17，收率0.21g(73％)，并将其立即用于络合物的制备。糖浆；1H-NMR(CDCl3,400MHz)δ7.35-7.21(20H,m,arom.H),4.52(2H,AB-sp.,Ha-CH2Ph,2Ja,b=12.1Hz),4.48(2H,AB～sp.,Hb-CH2Ph,2Ja,b=12.1Hz),4.43(2H,AB-sp.,Ha-CH2Ph,2Ja,b=12.1Hz),4.41(2H,AB-sp.,Hb-CH2Ph,2Ja,b=12.1Hz),3.61-3.41(8H,m,CH2O),2.29(2H,m,CH-P)；2.20(2H,m,CH-P)；2.07(4H,m,Ha-(CH2)2),1.53-1.23(8H,m,Hb-(CH2)2),(CH2)2)；13C-NMR(CDCl3,100MHz)δ138.6+138.4(ipso-C),128.3-127.3(arom.C),74.2(m,CH2Ph),72.9(CH2Ph),72.7(CH2O),70.2(CH2O),43.7(m,CH-P),40.0(m,CH-P),31.4(CH2),31.3(CH2),19.1(m,CH2)2)；31P-NMR(CDCl3,162 MHz):δ-6.9；
[Rh(COD)(P-P)]BF4络合物18、19及20的制备
0.3mmol双膦烷配位体13、14及17溶解在1.5mL THF中，并在-10℃的温度慢慢加入到0.122g(0.3mmol)[Rh(COD)2]BF4在3.5mL THF中的悬浮体中。约10min后，溶液在绝氧条件下过滤以去除不溶解成分，  然后加入15mL二乙醚。这导致分离出橙色沉淀或褐色油状物。滗析掉上层清液，然后以二乙醚洗涤2遍(每遍5mL)，减压干燥后获得NMR-光谱纯形式的橙色粉末。[Rh(COD)(13)]BF4(18)：收率225mg(73％)；1H-NMR(CDCl3,400MHz)δ7.70-6.80(24H,m,arom,H),5.76(2H,m,CHCOD),4.66(2H,m,CHCOD),4.42(2H,AB-sp.,Ha-CH2Ph,2Ja,b=12.3Hz),4.18(2H,AB-sp.,Hb-CH2Ph,2Ja,b=12.3Hz),4.05(2H,AB-sp.,Ha-CH2Ph,2Ja,b=12.9Hz),4.05(2H,AB-sp.,Hb-CH2Ph,2Ja,b=12.9Hz),3.80(2H,m,CH2O),3.60(4H,m,CH2O),3.30(2H,m,CH2O),2.87-1.50(20H,m,4×CH-P,4×(CH2)2)；13C-NMR(CDCl3,100MHz)δ140.5(m,Car-P),137.7+137.0(ipso-C),132.3,128.5-127.3(arom.C),107.0(CHCOD),91.9(CHCOD),73.2(m,CH2Ph),73.0(CH2Ph),70.6(m,CH2O),68.1(CH2O),49.7(m,CH-P),42.7(m,CH-P),33.7(CH2),32.1(CH2),31.3(CH2),27.0(CH2)；31P-NMR(CDCl3,162MHz):δ64.3(1JRh,p=150Hz)；MS(m/z；FABpos)941[M+-BF4](20),833[M+-BF4-COD](100)；[Rh(COD)(14)]BF4(19)：收率155mg(71％)；1H-NMR(CDCl3,400MHz)δ7.74(2H,m,arom.H),7.68(2H,m,arom.H),5.57(2H,m,CHCOD),4.80(2H,m,CHCOD),3.82(2H,m,CH2),3.67(2H,m,CH2),3.50(2H,m,CH2),3.26(6H,s,CH3O),3.13(2H,m,CH2),2.90(2H,m,CH-P),2.85(6H,s,CH3O),2.67-2.27(14H,m,CH-P,(CH2)2),1.94(2H,m,(CH2)2),1.58(2H,m,(CH2)2)；13C-NMR(CDCl3,100MHz)δ140.2(m,Car-P),132.4-132.0(arom.C),106.1(m,CHCOD),90.8(m,CHCOD),73.7(m,CH2O),70.8(CH2O),58.8+58.7(CH3O),49.4+42.5(m,CH-P),33.5+31.9+31.2+27.6(CH2)；31P-NMR(CDCl3,162MHz):δ65,0(1JRh,P=150Hz)；[Rh(COD)(17)]BF4(20)：收率190mg(65％)；1H-NMR(CDCl3,400MHz)δ7.30-7.05(20H,m,arom.H),5.55(2H,m,CHCOD),4.58(2H,m,CHCOD),4.43-4.20(8H,m,CH2Ph,3.77-3.40(8H,m,CH2O),2.50-1.90(20H,m,CH-P,(CH2)2)；1.60-1.20(4H,m,(CH2)2)；13C-NMR(CDCl3,100MHz)δ137.9+137.7(ipso-C),128.5-127.2(arom.C),102.1(CHCOD),91.5(CHCOD),73.4+72.1(CH2Ph),72.8(CH2O),68.8(CH2O),45.2+39.2(m,CH-P),32.7(CH2),31.3(CH2),30.0(CH2),27.7(CH2)20.8(m,CH2)2)；31P-NMR(CDCl3,162MHz):δ7.3(1JRh,P=147Hz)；
参考文献1 E.J.Corey；P.B. Hopkins Tetrahedron Lett.23(1982)1979-1982；2 M.Marzi；D.Misiti Tetrahedron Lett.30(1989)6075-6076；3 A.Haines Carbohydrate Res.1(1965)214-228；4 N.Machinaga；C.Kibayashi J.Org.Chem.57(1992)5178-5189；5 M.Marzi；P.Minetti；D.Misiti Tetrahedron 48(1992)10127-10132；
前手性被作用物的不对称氢化结果条件：被作用物：催化剂=100∶1，甲醇，25℃，1bar氢气；
Figure A9980630000161

Claims (9)

1．通式Ⅰ的膦烷或二膦烷
Figure A9980630000021
其中：
R是氢、C1～C6-烷基、芳基、烷芳基，SiR3 2，
R2是烷基或芳基，
A是氢、C1～C6-烷基、芳基、Cl或
Figure A9980630000022
B是2个磷原子之间的1～5个碳原子的连接基。
2．权利要求1的膦烷，其中R是氢或甲基。
3．权利要求1的二膦烷，其中取代基具有下列含义：
Figure A9980630000023
其中n=0,1,2,3,4或
Figure A9980630000024
其中m=0,1,2,3
R3=烷基或稠合芳基
4．权利要求3的二膦烷，其中取代基具有下列含义：
m=0,n=1。
5．一种金属络合物，  包含权利要求1～4中任何一项的膦烷以及选自Rh、Ru、Ir、Pd、Pt、Ni的中心原子。
6．权利要求5的金属络合物，其中选Rh或Ru作为中心原子。
7．权利要求5或6的金属络合物在不对称氢化、加氢甲酰基化、氢氰化、烯丙基取代以及由烯丙基胺到烯胺的异构化方面的应用。
8．一种化合物的不对称氢化方法，  包括待氢化原料化合物与氢气在权利要求5或6的金属络合物存在下进行反应。
9．权利要求8的方法，其中氢化是在1～2bar氢气压力下进行的。
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