CN1278801A - 基于手性胺噁唑啉基配位的过渡金属催化的反应 - Google Patents

基于手性胺噁唑啉基配位的过渡金属催化的反应 Download PDF

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CN1278801A
CN1278801A CN98811131A CN98811131A CN1278801A CN 1278801 A CN1278801 A CN 1278801A CN 98811131 A CN98811131 A CN 98811131A CN 98811131 A CN98811131 A CN 98811131A CN 1278801 A CN1278801 A CN 1278801A
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张绪穆
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Abstract

本发明涉及用于重要手性分子实用合成的新型过渡金属催化剂。该过渡金属催化剂含基于手性胺噁唑啉基配位体的手性配位体。本发明包括制备催化剂的方法以及用所述催化剂进行各种反应的方法。

Description

基于手性胺噁唑啉基配位体的过渡金属催化的反应
相关申请的相互参照
本申请要求1997年11月12日提交的美国专利临时申请60／065502的优先权，后者的全部内容作为参考并入。
发明背景
分子的手性在科学和技术中起重要的作用。许多药物、香料、食品添加剂和农用化学品的生物活性常常都与它们的绝对分子构型有关。虽然某一种对映体通过与天然的结合点相互作用而产生所希望的生物功能，但另一对映体通常没有相同的功能，甚至有时还有有害的副作用。制药工业对制备在对映体上纯形的手性药物的需求不断增长。为了完成这一吸引人的任务，化学家们已探索出许多途径来得到对映体纯的化合物，这些途径从天然存在的手性物质的旋光离析和结构改性到使用合成的手性催化剂和酶的不对称催化作用。在这些方法中，不对称催化作用或许是最有效的，因为可使用少量的手性催化剂来生产大量的手性目标分子。在最近数十年，很大的注意力放在发现新的不对称催化剂上，并有六个以上商业化的工业方法使用不对称催化作用作为生产对映体纯的化合物中的关键步骤。1997年全世界手性药物的规模差不多为900亿美元。
为了促进不对称反应，已制备了许多种手性膦。在这些配位体中，BINAP是最常用的二齿手性膦之一。已经证明，轴向不对称的全芳族BINAP对许多不对称反应是高度有效的。DUPHOS和有关的配位体在许多反应中也具有给人深刻印象的对映体选择性。但是，这些膦难以制备，其中一些易受空气影响。目前，广泛研究了用于不对称反应的手性含氮配位体。特别是，由手性氨基醇类得到的噁唑啉基化合物是通用的配位体。配位体和基质之间的二次相互作用的认别也用于不对称催化剂设计。例如，伯胺和仲胺可与基质形成H键。
发明概述
本发明的一个目的是研制适用于实用于不对称合成的有新一族胺噁唑啉基配位体的新型过渡金属络合物。在这里出现了几种用于不对称催化作用的新一族手性胺噁唑啉基配位体，包括仲胺噁唑啉基配位体和有一个以上噁唑啉基的胺噁唑啉基配位体。
本发明的另一目的是由手性氨基醇类制备手性噁唑啉基物质。
本发明的另一目的是发现适用于不对称催化作用的手性三齿和四齿配位体。特别是，已经证明这些配位体对于Ru催化的酮类和亚胺类的转移加氢是高度有效的。
本发明的另一目的是促进下述反应的、改进的过渡金属催化作用：加氢、加氢转移反应、加氢硅烷化、硼氢化、加氢乙烯基化、加氢甲酰化、加氢羧化、烯丙基烷基化、环丙烷化、狄尔斯－阿德尔反应、醛醇缩合反应、Heck反应、迈克尔加成反应和重排反应，从而得到生产重要手性药物和农用化学品的有效而实用的方法。
为了达到这些目的和根据这里具体化和广义描述的本发明的目的，本发明包括制备在不对称反应中具有高对映体选择性的催化剂的手性配位体，其结构选自下式(Ⅰ)至式(Ⅳ)的对映体：
Figure 9881113100091
Figure 9881113100101
式中R1、R2、R3、R4、R5、R6和R7各自独立为氢、烷基、芳基、取代的烷基或取代的芳基，其中R1、R2、R3和R4中任两个可彼此连接形成环状结构，其R5、R6和R7中任两个可彼此连接形成环状结构，以及其中n为1或2。
附图简介
图1为本发明一优选的实施方案中二(噁唑啉基甲基)胺(下文为“AMBOX”)配位体的一般合成途径。
图2为本发明优选实施方案的几种手性配位体的一般结构。
图3为本发明优选实施方案的手性配位体的具体例子。
图4为具有NH功能的手性三齿含氮配位体的过渡金属催化剂的图示说明，表示在前手性酮的转移加氢中得到的环状过渡状态。
优选实施方案的详述
用2－丙醇作为氢源的不对称催化转移加氢为不对称酮类还原成手性醇类提供了一条有吸引力的途径。在目前研制的有效过渡金属为基础的手性催化剂中，最值得注意的是R．Noyori等(“手性钌络合物催化的不对称转移加氢”，美国化学研究报告，第30卷，第2期，第97－102页(1997))和K．Haack等(“在钌助催化的醇类和酮类之间的不对称氢转移中的催化剂前体、催化剂和中间化合物”，应用化学，国际英文版，第36卷，第3期，第285－288页(1997))报导的Ru(Ⅱ)－TsDPEN(N－(对甲苯基磺酰基)－1，2－二苯基乙二胺)体系，在这里其内容作为参考并入。他们提出，配位体中的NH部分可通过氢键联到酮基质上，以促进环状过渡状态，大大提高基质对催化剂活性中心的亲合性，包括高的活性和旋光纯度。另一些报告已说明类似的“NH效应”，例如J．Gao等“用于芳族酮类不对称转移加氢的含C2不对称二膦／二胺四齿配位体的钌(Ⅱ)络合物”，有机金属，第15卷，第4期，第1087－1089页(1996)和P．Gamez等，“用C2不对称二胺作为手性配位体的羰基化合物的不对称催化还原”，四面体：不对称现象，第6卷，第3期，第705－718页(1995)，在这里其内容作为参考并入。
在研制用于不对称催化作用的手性三齿配位体的努力中，我们设计了二(聪唑啉基甲基)胺(“AMBOX”)配位体体系。手性三齿配位体一旦与过渡金属配位，则常常在金属中心周围形成深的手性穴。一个很好的例子是H．Nishiyama发现的大家熟悉的PYBOX配位体族，参见“手性的和C2不对称的二(噁唑啉基吡啶)铑(Ⅲ)络合物：酮类不对称加氢硅烷化的有效催化剂”，有机金属，第8卷，第3期，第846－848页(1989年3月)。这种催化剂已成功地用于不对称反应的催化作用。PYBOX的噁唑啉环上的两个R基团形成高度对映体选择性的“手性栅栏”，它能更好地区分面向基质的Re和Si面。
用胺功能取代PYBOX的吡啶骨架，新的配位体AMBOX类似上述Noyori和Haack文章中提出的经受环状过渡状态，并有效地催化不对称转移－－例如酮类的加氢转移还原。图4为前手性的酮类的转移加氢中得到的环状过渡状态的图示说明。
图1说明本发明一优选的实施方案，二[4－(R)－苯基噁唑啉-2-基甲基]胺(下文简称为“(R)－Ph-AMBOX”)的一条优选的合成途径。氰胺在a处与HCl和甲醇反应，生成盐酸亚胺酯，粗产率为76％。得到的盐酸亚胺酯在未进一步纯化的条件下、在b处与二氯甲烷中的(R)-苯基甘氨醇(glycinol)在0℃至室温下反应12小时。制得(R)－Ph－AMBOX，产率15％。
可通过在步骤b选择不同的氨基醇来决定噁唑啉基胺产物的手性以及取代基的特性。例如，为了形成图3中所示的优选结构X1，可在步骤b中使用下式氨基醇。在图1所示的图示
Figure 9881113100121
中，可使用(S)氨基醇来得到有相对手性的产物。
本发明的催化剂通过这里描述的胺－噁唑啉基配位体与过渡金属络合来制备。对于熟悉本专业的普通技术人员来说，适合与本发明的手性配位体络合的过渡金属催化剂前体是已知的。例如，可使用[Rh(cod)Cl]2、[Rh(cod)2]X、[Ir(cod)Cl]2、[Ir(cod)2]X、Ru(cod)Cl2，其中“cod”为1，5－环辛二烯和X为BF4、ClO4、SbF6、CF3SO3或等价物。另一方面，也可使用RuCl2(PPh3)3、RuHCl(PPh3)3、RuX2(PR3)3、RuHX(PR3)3、RuX2和其他等价物，其中X为卤素，R为取代的或未取代的烷基或芳基。
催化剂的优化
使用AMBOX和各种商业使用的过渡金属前体就地制备的催化剂，对2－丙醇中的苯乙酮的转移加氢的最初试验结果是令人失望的。所有这些催化剂都只有较差的对映体选择性，用RuCl2(PPh3)3得到的最高对映体过量(在这里另称为“ee”)小于50％。
表1列出使用(R)－Ph－AMBOX对苯乙酮转移加氢催化条件优化的结果。下面的反应(1)在5毫升2－丙醇的0．1摩尔浓度苯乙酮溶液中进行。酮：R11 u：(R)－Ph－AMBOX的比例为100∶1∶1．1。
表1
项目 游离PPh3 NaOPri当量b     T℃     t小时 产率c％     eec
    1d2e345678     +++－－－－－     15151．01．00．502．01．0     8282828282828282   0．50．02510．17110．1722     969267912609491     4560849795N／A6895
 a．“+”表示反应混合物中存在游离PPh3；“－”表示催化剂制成后
游离的PPh3在加入苯乙酮和NaOPri以前用乙醚洗出b．基于 R u 11 的当量c．用手性Supelco β－DEX 120毛细管色谱柱，用气相色谱分析测
定产率％和对映体过量％。通过旋光旋转与文献值比较来确定绝
对构型。所有的主要二次醇产物为(S)异构体。d．通过室温下将R－(Ph)－AMBOX和RuCl2(PPh3)3的混合物搅拌过夜
制备的催化剂。e．对于2—8项，催化剂通过R－(Ph)－AMBOX和RuCl2(PPh3)3在82
℃下回流2小时来制备。
已发现，通过AMBOX和RuCl2(PPh3)3在2－丙醇中回流就地制备的催化剂远比在室温下制备的催化剂更加有效。从表1中的第2和8项可以看出，催化剂通过RuCl2(PPh3)3前体在82℃下回流2小时制备。这些催化剂比对应第1项的催化剂得到更大的对映体过量，后一催化剂在室温下过夜制备。因此，根据本发明的一优选的实施方案，催化剂通过在2－丙醇的沸点下回流来制备。
可显著增加催化活性和对映体选择性的另一因素是在加入苯乙酮和碱(NaOPri)以前除去在AMBOX络合过程中释放的游离三苯基膦配位体。由于游离的PPh3能与Ru中心再次络合，所以它可能干扰反应。游离PPh3的除去减少了对对映体选择性催化过程的不利竞争。根据本发明，RuCl2(PPh3)3前体的混合物优选与R－Ph－AMBOX一起加热2小时，生成一种绿色的溶液。在真空下除去溶剂以后，用乙醚洗涤生成的浅绿色残留物，以便除去所有的游离PPh3。再次将固体溶于2－丙醇，接着加入基质和NaOPri。经这样的处理，对映体过量从84％显著增加到97％，正如从表1中项目3和4的比较可看出的。
可提高活性和对映体选择性的另一重要因素是NaOPri对催化剂的摩尔比。这一比例应为1．0左右。当使用0．5摩尔当量的碱时，反应变得很缓慢，虽然对映体过量仍很高(表1第5项)。当使用2．0摩尔当量的碱时，反应加快，但伴随着对映体过量的严重损失(表1第7项)。
图4说明假设的活性催化剂的结构，其中L表示PPh3，X表示氯。图4的催化剂可能通过以下步骤形成：一个HCl被一个NaOPri从假设的RuCl2PPh3前体(AMBOX)中抽出后，接着从2－丙醇中除去一个质子和一个氢根。在顶上的PPh3对面的氯根应优选与NH质子一起除去，这是考虑到了PPh3的强的转移作用。但是，如果加入1摩尔当量以上的碱，在NH对面的氯根也可能被除去，得到有利于酮还原的逆反应的可能途径，因此迅速失去对映体过量。由于游离的PPh3能与钌中心再次络合，所以它也可能干扰反应。所以，游离PPh3的除去应看成是减少对映体选择性的催化过程的不利竞争。的确，经这样的处理，对映体过量从84％显著增加到97％。(看表1中的第3－4项)。
表2说明在优化的条件下，使用本发明的催化剂，各种芳族酮还原成它们的仲醇，并有高的对映体过量和很满意的产率。通用反应(2)使用5毫升2－丙醇中的0．1摩尔浓度酮溶液进行(除非另加说明)。酮∶Rn∶(R)－Ph－AMBOX∶NaOPri的比例为100∶1∶1．1∶1．0。
基质和催化反应条件的各种变化列入下表2。
表2
Figure 9881113100152
Figure 9881113100161
a．产率％和对映体过量％用气相色谱法测定，使用手性的supelco β—DEX 120毛细管色谱柱。绝对构型通过旋光旋转与文献值比较来测定。所有主要的二次醇产物为(S)异构体。
对映体过量和化学产率受到基质的空间性质和电子性质的敏感影响。当比较甲基酮、乙基酮和异丙基酮的结果时，酮的烷基侧链的空间阻碍作用是很明显的(表2第1－3项)。通过用甲氧基代替氯根对位的取代基，对映体过量提高但转化率惊人下降(表2第11、12项)。对于大多数试验的酮，特别是邻位甲基－和邻位氯－取代的苯乙酮，随着转化率的提高，产物对映体过量的下降是中等的，在整个反应期间几乎没有看到任何下降(表2第4、5项)。但是，苯基的邻位基是甲氧基时，得到很差的结果(表2第6项)。
图2的式(Ⅰ)至(Ⅳ)为本发明优选配位体的非限制性例子。正如在图2中看出的，本发明所有优选的配位体都含有在两个位置用烷基胺或取代的烷基胺取代的噁唑。正如在式(Ⅰ)中看出的，在噁唑的2位上取代的烷基胺例如可为甲基胺或取代的甲基胺。而且，正如在图2中所示，胺可为伯胺、仲胺或叔胺。
在图2中，R1、R2、R3、R4、R5、R6和R7可为相同的或不同的，它们可为氢、烷基、芳基、取代烷基或取代芳基。这样的实施方案也在本发明的范围内，其中R1、R2、R3和R4中任两个可连接形成一环状结构，以及其中R5、R6和R7中任两个可连接形成一环状结构。例如，在式(Ⅱ)中，R1和R3为甲基，R2和R4为苯基，形成具有式(Ⅺ)构型的结构。同样，熟悉本专业的一般技术人员会认识到，通过式(Ⅰ)至(Ⅳ)中R1至R4连接可能构成许多种环状结构物。另一方面，通过R5和R6连接形成的环可形成类似式(Ⅵ)中所示的结构。
虽然在图中仅示出某些对映体构型，但在合成过程中使用不同的试剂可控制配位体的对映体取向。所列分子式的对映体也在本发明的范围内。
图3中的图(Ⅴ)至(Ⅺ)表示本发明的手性胺噁唑啉配位体的特别优选实施方案，例如噁唑啉－2－基甲基胺，正如式(Ⅴ)中所示，它可在噁唑或甲基上被取代；或者2－噁唑啉－2－基氮杂环戊烷，正如式(Ⅵ)中所示，它可在噁唑上被取代；或者上述的二[4－(R)－苯基噁唑啉－2－基－甲基]胺，它可由式(Ⅶ)得到。
总之，本发明包括新型的手性三齿配位体，它们与RuCl2(PPh3)3和其他催化剂前体形成对各种酮的转移加氢和其他反应呈高效的催化剂。

Claims (20)

1．一种手性配位体，用它制成在不对称反应中有高对映体选择性的催化剂，它具有选自下式(Ⅰ)至(Ⅳ)的对映体结构： 式中，R1、R2、R3、R4、R5、R6和R7各自独立为氢、烷基、芳基、取代烷基或取代芳基，其中R1、R2、R3和R4中任意两个可相互连接形成一个环状结构，其中R5、R6或R7中任意两个可相互连接形成一个环状结构，且其中n为1或2。
2．根据权利要求1的手性配位体，其中所述的配位体与过渡金属络合。
3．根据权利要求2的手性配位体，其中所述的过渡金属选自铑、铱、钌和钯。
4．根据权利要求1的手性配位体，其中所述的配位体与选自[Rh(cod)Cl]2、[Rh(cod)2]X、[Ir(cod)Cl]2、[Ir(cod)2]X、Ru(cod)Cl2的过渡金属催化剂前体络合，其中cod为1，5－环辛二烯，X为BF4、ClO4、SbF6或CF3SO3。
5．根据权利要求1的手性配位体，其中所述的配位体与选自RuCl2(PPh3)3、RuHCl(PPh3)3、RuX2(PR3)3、RuHX(PR3)3、RuX2的过渡金属催化剂前体络合，其中X为卤素，R为取代的或未取代的烷基或芳基。
6．根据权利要求1的手性配位体，其中所述的配位体选自下式(Ⅴ)至(Ⅺ)：
7．一种手性配位体，用它制成在不对称反应中有高对映体选择性的催化剂，所述的手性配位体含二(噁唑啉基)胺。
8．根据权利要求1的手性配位体，其中所述的配位体为二[4－(R)－苯基噁唑啉－2－基－甲基]胺。
9．一种制备在不对称反应中有高对映体选择性的催化剂的方法，该方法包括，用手性醇还原亚胺酯，制得权利要求1的手性配位体。
10．根据权利要求9的方法，其中还包括，使所述的手性配位体与含过渡金属的催化剂前体络合。
11．根据权利要求10的催化剂制备方法，其中，所述的催化剂前体还含三苯基膦，以及其中所述的制备催化剂的方法包括，除去在手性配位体与催化剂前体络合过程中释放出的三苯基膦。
12．根据权利要求10的催化剂制备方法，其中所述的催化剂前体和所述的手性配位体与醇在醇的回流温度下回流。
13．根据权利要求10的催化剂制备方法，其中所述的过渡金属选自铑、铱、钌和钯。
14．根据权利要求10的催化剂制备方法，其中所述的催化剂前体选自[Rh(cod)Cl]2、[Rh(cod)2]X、[Ir(cod)Cl]2、[Ir(cod)2]X，其中cod为1，5－环辛二烯和X为BF4、ClO4、SbF6或CF3SO3。
15．根据权利要求10的催化剂制备方法，其中所述的催化剂前体选自RuCl2(PPh3)3、RuHCl(PPh3)3、RuX2(PR3)3、RuHX(PR3)3、RuX2 ，其中X为卤素，R为取代的或未取代的烷基或芳基。
16．一种提高化学反应中对映体选择性的方法，该方法包括，使基质与含权利要求1的手性配位体的催化剂接触。
17．根据权利要求16的方法，其中所述的反应选自加氢、加氢转移反应、加氢硅烷化、硼氢化、加氢乙烯基化、加氢甲酰化、加氢羧化、烯丙基烷基化、环丙烷化、狄尔斯－阿德尔反应、醛醇缩合反应、Heck反应、迈克尔加成反应和重排。
18．根据权利要求17的方法，其中所述的反应为转移加氢，而所述的基质为酮或亚胺。
19．根据权利要求18的方法，其中基质与催化剂的接触还包括，使所述的基质和所述的催化剂与碱接触，其中所述的碱与所述的催化剂的摩尔比为0．5－2．0。
20．根据权利要求19的方法，其中所述的摩尔比约为1．0。
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