CN1008095B - 手性铑二膦络合物的制备 - Google Patents

手性铑二膦络合物的制备

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CN1008095B
CN1008095B CN86106525.5A CN86106525A CN1008095B CN 1008095 B CN1008095 B CN 1008095B CN 86106525 A CN86106525 A CN 86106525A CN 1008095 B CN1008095 B CN 1008095B
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埃米尔·阿尔宾·布罗格尔
伊沃·克拉默里
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F Hoffmann La Roche AG
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Abstract

本发明描述了如下一般化学式的新颖手性铑—二膦络合物:
[Rh(X)(Y)(Lo,1,2)]1,2
其中X、Y和L具有权利要求1所描述的含意。而且,描述了这些络合物的制造方法及它们在不对称氢化作用方面的应用。

Description

本发明涉及到如下通式Ⅰ的新颖手性铑-二膦络合物:
其中也可以固定到载体上的X代表化学式Z-COO-的残基,残基中的Z表示下面的基团或芳基,
其中R1、R2、R3=氢、卤素、低级烷基、芳基-低级烷基、全氟-C1-20-烷基、芳基或基团-OR7、-(CH2n-COA或AOC-(CF2n,但R1、R2和R3中必须至少有一个代表-OR7或芳基,
R4、R5、R6=氢、卤素、低级烷基、芳基-低级烷基、全氟-C1-20-烷基、芳基或基团-(CH2n-COA或AOC-(CF2n
R7=氢、低级烷基、部分地或全部被卤化的低级烷基、芳基或芳基-低级烷基,
A=残基-OR或-NR 2
R=氢、低级烷基、芳基、芳基-低级烷基或一种阳离子,
R′=氢、低级烷基、芳基或芳基-低级烷基和
n=0~20,和其中:
Y代表一种手性二膦配位体,其通式如下:
Figure 86106525_IMG7
其中R3代表芳基和R9代表基团-CO-R10,-SO2-R10、-PO(R102或者-PS(R102,其中R10表示芳基、低级烷基、二-芳氨基、二-低级烷基氨基、芳氧基或低级烷氧基,
和L代表可易于交换的中性的配位体,例如链烯、腈类或反应中所采用的溶剂,
但式Ⅰ中这样一些络合物除外,即其中也可以固定到载体上的X代表化学式Z-COO-的残基,残基Z表示基团
Figure 86106525_IMG8
全氟苯基、全氟二苯基或为下面化学式的一种残基:
Figure 86106525_IMG9
以及R1、R2和R3代表卤素、低级烷基、全氟苯基、全氟-C1-20-烷基、氢或基团-COA或AOC-(CF2n-,其中A表示残基-OR或-NR 2,但取代基R1、R2和R3中必须至少有一个表示氟,R表示氢、低级烷基或一种阳离子,R′表示氢或低级烷基和n表示1-20的数。
本发明也涉及化学式Ⅰ的铑-二膦络合物的制造及其在不对称氢化作用方面的应用。
从文献资料中已经知道手性铑-二膦络合物及它们在不对称的氢化作用方面的应用。这些络合物通常是阳离子的,或当它们为中性时,含有作为配位体X的氯、溴或碘。这些络合物用于不对称氢化作用时所达到的光学收率处于最有利的情况,就酮泛内酯(Ketopa-ntolactone)的氢化作用来说,大约为80-84%。
现在意外地发现,与早先已知的络合物比较,本发明通式(Ⅰ)的铑-二膦络合物是颇有效的和颇有对映选择的,尤其是,这意味着当采用这些络合物时可以使用相当少量的催化剂,反应的时间也有可能缩短,以及光学收率可以达到95%以上。
术语“低级烷基”在本发明的范围内表示直链的或具有1-9个碳原子的支链烷基团,例如甲基、乙基、丙基、异丙基、正-丁基、异丁基、叔丁基、戊基、己基、庚基、辛基、壬基等等。术语“卤素”表示氟、氯、溴和碘,以及氟为最佳。术语“全氟-C1-20-烷基”在本发明范围内表示不但是直链的,而且是支链的,还可能有光学活性,因此不是所有的氢原子需要被氟原子置换。于是,当不是所有的氢原子被氟原子置换时,尤其,在末端的氢原子是经常存在的。就X固定到载体上这一点来说,这是通过基团-COA来实现的。
关于化学式(Ⅰ)的化合物所使用的术语“芳基”在本发明的范围内,不但表示芳烃,而且表示具有4-14个碳原子的芳香杂环。尤其可以把氧和氮考虑为杂原子。而且这些环既可以是未取代的,又可以是取代的,在那种情况下最好把卤素、羟基、低级烷基、全氟-低级烷基、低级烷氧基和甲酰考虑为取代基。并且所存在的芳基可以与过渡金属,例如铬、铁或镍络合。
关于化学式Ⅱ的化合物在下文所用的术语“芳基”在本发明范围内表示苯基,该苯基可以任意地具有对-和/或间-位低级烷基或低级烷氧基、最好是甲基或甲氧基,或二-低级烷氨基,最好是二甲基氨基,以及羧基、氨基甲酰基、氰基或低级烷氧基羰基。而且,在相同磷原子上的二个芳基通过邻-位置或也可通过亚甲基、氧基或亚丙基团相互直接连接。术语“芳氧基”表示表示一种基团,其中芳基残基具有上述的含意。
术语“低级烷氧基”表示基团,其中烷基残基具有上述的含意。并且,符号“
Figure 86106525_IMG10
”表示该相应的残基位于该分子平面之上,而符号“
Figure 86106525_IMG11
”表示相应残基位于该分子平面之下。符号n代表0-20的数字,较好为1-12,最好为1-8。
术语“中性配位体”在本发明的范围内的表示可易于交换的配位体,例如链烯,比如乙烯、丙烯、环辛烯、1,5-己二烯、降冰片二烯、1,5-环辛二烯等等;一种腈比如乙腈和苄腈或也就是所采用的溶剂等等。在氢化作用的情况下,该配位体可以是易交换的。在这种配位体有一个以上的情况下,这些配位体也可以是相互不同的。
在不对称氢化作用方面所已知的和也可以任意地固定到载体上的任何二膦配位体基本上可被用作手性二膦配位体。这种配位体是大家 都知道的而且为本技术领域的人所容易理解的。例如,在本发明范围内所考虑的配位体出自下面的文献:马科.L.等著,“均相催化的特性”1981年第4期,P145-202,1978年4月6日的日本专利申请号67411(德温特8180C);西德公开说明书No2161200;欧洲专利公布号104375。特别合适的和最佳的配位体是手性膦,其一般化学式如下:
Figure 86106525_IMG12
其中R8代表芳基,R9代表基团-CO-R10,-SO2-R10,-PO(R102或-PS(R102,其中R10表示芳基、低级烷基、二-芳氨基、二-低级烷基氨基、芳氧基或低级烷氧基。
化学式Ⅰ的最佳铑二膦的络合物是那些其中Z代表基团
的络合物并且R1、R2和R3取代基中的一个表示残基-OR7,其他二个表示氟、氢、全氟-C1-20-烷基或者芳基,以及那些其中R1、R2和R3取代基中的一个代表芳基,其他二个代表氟、氢或全氟 -C1-20-烷基,但它们其中必须至少有一个表示氟。在配位体X为手性的情况下,该配位体可以以外消旋形式存在,或最好以光学活性形式存在。
化学式Ⅱ的最佳二膦配位体是那些其中R8代表苯基、对-甲苯基、间-甲苯基、或3,5-二甲苯基,以及R9残基中的R10表示苯基,对-甲苯基、间-甲苯基、对-低级烷氧基羰基苯基或叔-丁氧基。并且特别最佳的膦类是那些其中R9残基代表-PO(R102基团。下面可以举出一些最佳二膦配位体的实例:
(2S,4S)-4-(二-间-甲苯基膦基)-2-〔(二-间-甲苯基膦基)甲基〕-1-(二苯基膦酰基)-吡咯烷(mcH3-POPPM);
(2S,4S)-4-(二苯基膦基)-2-〔(二苯膦基)-甲基〕-1-(二苯基膦酰基)-吡咯烷;(POPPM);
(2S,4S)-4-(二-对-甲苯基膦基)-2-〔(二-对-甲苯基膦基)甲基〕-1-(二苯基膦酰基)吡咯烷;(PCH3-POPPM);
(2S,4S)-4-(二苯基膦基)-2-〔(二苯基膦基)-甲基〕-1-(二-对-甲氧甲酰苯基膦)-吡咯烷;
(2S,4S)-4-(二苯基膦基)-2-〔(二苯基膦基)-甲基〕-1-(叔丁氧基羰基)-吡咯烷(BPPM);
(2S,4S)-4-(二-间-甲苯基膦基)-2-〔(二-间-甲苯基膦基)甲基〕-1-(叔丁氧基羰基)-吡咯烷(mcH3-BPPM)。
化学式Ⅰ的特别最佳的铑二膦络合物是那些其中R1、R2和R3取代基中的一个表示残基-OR7,其他二个表示氟或一个表示三氟甲基和另一个表示苯基,以及那些其中R1、R2、和R3取代基中的一个代表苯基,其他二个代表氟或一个表示氢和另一个表示氟,该二膦配 位体是mcH3-POPPM。如下化学式的络合物是最最佳的:
可以用一个本身为已知的方法来制造本发明化学式Ⅰ的铑-二膦络合物。例如可以按下面一些反应来制造这些络合物:
a)化学式(Ⅲ)的铑络合物与手性二膦配位体反应,
其中X和L具有与前面相同的含意,m表示1-4的数;
b)化学式(Ⅳ)的铑络合物与手性二膦配位体及含阴离子X的盐反应,
其中L和m具有与前面相同的含意,A-代表阴离子,特别BF-,ClO- 4,PF- 6或B(C6H5- 4;
c)化学式(Ⅴ)的铑-二膦络合物与含阴离子X的盐反应,
其中L,Y和A-有与前面相同的含意,P代表1-3的数;
d)化学式(Ⅵ)的手性铑-二膦络合物与化学式(Ⅶ)的银盐或铊盐反应,
Ag-X或T1-X    Ⅶ
其中X表示卤素,L和Y具有与前面相同的含意,
其中X具有与前面相同的含意。
化学式Ⅲ、Ⅳ、Ⅴ和Ⅵ的铑络合物的反应可以用某种已知的方法按a-d不同的反应来进行。这在某种惰性的有机溶剂中进行很方便。下面可列举这些溶剂的实例:芳香烃例如苯、甲苯等,酯类例如乙酸乙酯等,环醚类例如四氢呋喃或二噁烷、低级醇类例如甲醇、乙醇诸如此类或也可以为其混合物。该反应可以大约在0°-100℃的温度范围内进行,最佳的温度大约在15°-60℃范围内,但是氧被严格地排除。
术语“含阴离子X盐”在本发明范围内特别表示铵盐、碱金属盐,碱土金属盐以及其他合适的金属盐类。这些盐类均属于已知的物质。如果需要增加这种盐类在某些溶剂中的溶解度,那么可以添加一种合适的冠醚。
化学式Ⅰ的铑-二膦络合物都是催化剂或其前体。因为不能肯定地给出它们准确的化学结构,所以铑-二膦络合物的特征也在于:按上述a)到d)的反应进行化学式Ⅲ-Ⅵ的铑络合物反应,它们是可以获得的。
用作原材料的化学式Ⅲ、Ⅳ、Ⅴ和Ⅵ的铑络合物均属于已知物质或类似的已知物质,这种类似的已知物质可容易地由类似于已知的物质来制备。
正如已经所提到的,本发明化学式Ⅰ的铑-二膦络合物可以用作不对称氢化作用中的催化剂。它们在α、β-不饱和酸和酯类、α-酮-羧酸和酯类以及α-酮-内酯类的不对称氢化作用方面是特别重要的。尤其关于把二氢-4,4-二甲基-2,3-呋喃二酮(酮泛内酯)(Ketopantolactone)不对称氢化成相应的R-(α-羟基-β,β-二甲基-γ-丁内酯)〔R-(-)-泛内酯(Pantolactone)〕 显得很重要。
因此,为了进行上述不对称的氢化作用,可把化学式Ⅰ的络合物加到一种被氢化的不对称化合物的溶液中去。换句话说,在有被氢化的不对称化合物的情况下,也能就地产生不对称的氢化作用。
不对称氢化作用可以在合适的有机溶剂中进行,那些有机溶剂在其反应条件下是惰性的。照这样,下面的一些有机溶剂有可能被指定为溶剂:尤其是低级烷醇例如甲醇或乙醇,芳香烃例如苯或甲苯,环醚例如四氢呋喃或二噁烷,酯类例如乙酸乙酯或者其混合物,诸如此类,铑和配位体Y的克分子比约适合在0.05-5之间,但最好约在0.5-2。铑和残基X的克分子比约适合在0.01-20之间,但最佳约在0.5-10之间。化学式Ⅰ的铑络合物和被氢化的化合物重量百分数的比约适合在0.00001-5之间,但最好约在0.0001-0.01之间。
采用化学式Ⅰ的络合物适宜于大约在0℃-100℃温度情况下进行不对称的氢化作用。但最好温度约在20℃-70℃。在压力下,便于完成这些氢化作用,特别约在1-100巴的压力下,但最佳压力为2-50巴。
下面一些实例用来说明本发明,但决非受其限制。
在这些实例中,一些缩略语含有如下的含意:
COD=1,5-环辛二烯
BPPM;mCH3-POPPM;为第6-7页上所提到的-二膦类
在25米毛细管柱上,用手性物相(Chiral    Phase)(sP-300)通过(R)-和(S)-泛内酯的气相色谱法的测定来测量对映体组合物(对映体过量允许误差)。在几种情况下,在温度20℃和浓度 3%的去离子水中,以589毫微米(D-线)来测定(R)-(-)-泛内酯的旋光度。最纯的(R)-(-)-泛内酯的光纯度值为〔α〕=-51.6°(C=3,H2O)。
实施例1
将100毫升玻璃烧瓶置于一个手套箱中(含量<1ppm),悬浮在手套箱中的该玻璃烧瓶内有含水的40%四丁铵氢氧化物溶液254.2毫克(0.389毫摩尔)、全氟苯氧基乙酸108.2毫克(0.389毫摩尔)、双-(1,5-环辛二烯)-铑(1)四氟硼酸盐157.8毫克(0.389毫摩尔)和(2S,4S)-4-(二-间-甲苯基膦基)-2-〔(二-间-甲苯基膦基)甲基〕-1-二苯基膦酰基-吡咯烷(mCH3-POPPM)281.7毫克(0.389毫摩尔)。它们悬浮于50毫升甲苯中。随后将此混悬浮液22-25℃搅拌16个小时,从而形成一种几乎透明的橙红色的催化剂溶液。
实施例2
把40克(0.31摩尔)酮泛内酯、160毫升甲苯和根据实施例1制备的50毫升催化剂溶于注入手套箱内的500毫升的高压釜中(含氧量<1ppm)。在40℃和40巴恒压氢的条件下进行氢化,并且在氢化的同时加以强烈地搅拌。1小时后该转化率为99.8%。经过4小时的总氢化时间后,黄色氢化溶液从高压釜中倾倒出来,随后高压釜用甲苯漂洗三次,每次用50毫升甲苯。在60℃、17毫巴的条件下,该化合物的甲苯溶液在旋转式汽化器上进行蒸发。在130-150℃(蒸浴温度)和12毫巴情况下,蒸馏42克残余物。最后得到具有92.8%(允许误差)的光学纯度的40.3克(99.3%)(R)-α-羟基-β,β-二甲基-γ-丁内酯〔(R)-(-)-泛内酯〕。
实施例3-29
用类似于实施例1的方法制备催化剂溶液,尔后按类似于实施例2的方法进行酮泛内酯的氢化作用。这些结果汇编在下面的表中。
Figure 86106525_IMG14
Figure 86106525_IMG15
Figure 86106525_IMG16
实施例30
置于手套箱中的钢质高压釜内(含氧量<1ppm)注入的物质有:异丙基α-氧代-γ-(1.3-二氧-2-异氮杂茚基)-丁酸酯30克(0.104摩尔)、甲苯110毫升和催化剂溶液,这种催化剂溶液是由如下物质按类似于实施例1的方法制备而成的:含40%四丁铵氢氧化物溶液165克(0.292毫摩尔)、(S)-α-甲氧基-α-三氟甲基苯乙酸68.3毫克(0.292毫摩尔)、双-(1,5-环辛二烯)-铑(1)四氟硼酸酯118.4毫克(0.292毫摩尔)和(2S,4S)-1-叔丁氧基羰基-4-二苯基膦基-2-二苯基膦基甲基-吡咯烷164.7毫克(0.292毫摩尔)。在40℃和10巴恒压氢的条件下进行氢化,并且在氢化的同时强烈地搅拌24小时。蒸发氢化溶液,用硅胶对该残余物进行色谱分析,并且蒸发含有成品的馏分。最终获得29.5克(97.4%)异丙基(R)-α-羟基-γ-(1,3-二氧-2-异氮茚基)-丁酸酯,为淡黄色的晶体。熔点为78-82℃,对映体纯度为78.5%(如同莰烷酸酯,在21米毛细管柱Se54〕上按气相色谱法测定)。〔α〕20 D=-4.4°(C=1,CH3OH);光学纯度79.0%。

Claims (6)

1、一种制造下述通式Ⅰ的手性铑-二膦络合物的方法,
其中也可以固定在载体上的X代表化学式Z-COO-的残基,残基中Z代表下面的基团:
Figure 86106525_IMG1
或芳基,其中
R1、R2、R3=氢、卤素、低级烷基、芳基-低级烷基、全氟-C1-20-烷基、芳基或基团-OR7、-(CH2)n-COA或AOC-(CF2)n,但R1、R2、和R3中必须至少有一个代表-OR7或芳基,
R4、R5、R6=氢、卤素、低级烷基、芳基-低级烷基、全氟-C1-20-烷基、芳基或基团-(CH2)n-COA或AOC-(CF2)n,
R7=氢、低级烷基、部分或全部地卤化的低级烷基、芳基或芳基-低级烷基,
A=残基-OR或-NR 2
R=氢、低级烷基、芳基、芳基-低级烷基或一种阳离子,
R′=氢、低级烷基、芳基或芳基-低级烷基和
n=0-20,和其中:
Y代表一种手性二膦配位体,其通式如下:
其中R8代表芳基和R9代表基团-CO-R10,-SO2-R10、-PO(R10)2或者-PS(R10)2,其中R10表示芳基、低级烷基、二-芳氨基、二-低级烷基氨基、芳氧基或低级烷氧基,
L代表可易于交换的中性的配位体,例如链烯、腈类或反应中所采用的溶剂,
但式Ⅰ中这样一些络合物除外,即其中也可以固定到载体上的X代表化学式Z-COO-的残基,残基中Z表示下面的基团:
Figure 86106525_IMG3
全氟苯基、全氟二苯基或为下面化学式的一种残基:
Figure 86106525_IMG4
以及R1、R2和R3代表卤素、低级烷基、全氟苯基、全氟-C1-20-烷基、氢或基团-COA或AOC-(CF2)n-,其中A表示残基-OR或-NR 2,但取代基R1、R2和R3中必须至少有一个表示氟,R表示氢、低级烷基或一种阳离子,R′表示氢或低级烷基和n表示1-20,
此方法包括:
a)化学式[Rh(X)(Lm)]1,2 Ⅲ
的铑络合物与手性二膦配位体Y反应,
其中X和L具有与前述相同的含意,m表示1-4的数;或
b)化学式[Rh(Lm+1)]+A-
的络合物与手性二膦配位体Y及阴离子X的盐反应,
其中L和m具有与前述相同的含意,A-代表阴离子,特别是BF- 4、CLO- 4、PF- 6或B(C6H5)- 4;或
c)化学式[Rh(Lp)(Y)]+A-
的铑-二膦络合物与含阴离子X的盐反应,
其中L、Y和A-具有与前述相同的含意,P代表1-3的数;或
d)化学式[Rh(X1)(L1,2)(Y)] Ⅵ
的手性铑-二膦络合物与
化学式  Ag-X或Tl-X  Ⅶ
的银盐或铊盐反应,
其中X1表示卤素,L和Y具有与前述相同的含意,
其中X具有与前述相同的含意。
2、根据权利要求1所述的方法,其中所用原料和产物中X的含意为Z代表下面的基团:
Figure 86106525_IMG5
和R1、R2和R3与权利要求1所述相同。
3、根据权利要求2所述的方法,其中原料中的取代基R1、R2和R3中的一个表示残基-OR7和其他两个表示氟、氢、全氟-C1-20-烷基或芳基,以及R7与权利要求1所述相同。
4、根据权利要求2所述的方法,其中原料中的取代基R1、R2和R3中的一个表示苯基和其他两个代表氟、氢或全氟-C1-20-烷基,但它们至少有一个表示氟。
5、根据权利要求1所述的方法,其中原料中的R9代表基团-PO(R102
6、根据权利要求5所述的方法,其中原料中的R8表示苯基、对-甲苯基、间-甲苯基或3,5-二甲苯基,以及R10表示苯基、对-甲苯基、间-甲苯基、对-低级烷氧羰基苯基或叔丁氧基。
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