CN108602846A - 用于产生乙基多杀菌素的选择性催化剂 - Google Patents

用于产生乙基多杀菌素的选择性催化剂 Download PDF

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CN108602846A
CN108602846A CN201780010174.8A CN201780010174A CN108602846A CN 108602846 A CN108602846 A CN 108602846A CN 201780010174 A CN201780010174 A CN 201780010174A CN 108602846 A CN108602846 A CN 108602846A
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ethyl pleocidin
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T·J·福斯奇
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Kedihua Agricultural Technology Co ltd
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Abstract

本发明基于以下发现：与先前方法相比，非均相催化剂[Rh(C2H4)2Cl]2和/或[Rh(COD)2][BF4]可用于以较低的催化剂负载量产生较高收率的乙基多杀菌素。此外，也可添加一种或多种磷配体供体，以进一步提高收率/效率。本文提供的方法和/或体系使得能够以具有成本效益的方式以相对简单的工序大量产生乙基多杀菌素。

Description

用于产生乙基多杀菌素的选择性催化剂
相关申请的交叉引用
本申请要求2016年3月4日提交的美国临时专利申请序列号62/303,407的权益。
背景技术
乙基多杀菌素是(2R,3aR,5aR,5bS,9S,13S,14R,16aS,16bR)-2-(6-脱氧-3-O-乙基-2,4-二-O-甲基-α-L-甘露吡喃糖氧基)-13-[(2R,5S,6R)-5-(二甲基氨基)四氢-6-甲基吡喃-2-基氧基]-9-乙基-2,3,3a,4,5,5a,5b,6,9,10,11,12,13,14,16a,16b-十六氢-14-甲基-1H-as-苯并二茚并[3,2-d]氧杂环十二碳六烯-7,15-二酮(也称为“二氢-Et-J”)和(2R,3aR,5aS,5bS,9S,13S,14R,16aS,16bS)-2-(6-脱氧-3-O-乙基-2,4-二-O-甲基-α-L-甘露吡喃糖氧基)-13-[(2R,5S,6R)-5-(二甲基氨基)四氢-6-甲基吡喃-2-基氧基]-9-乙基-2,3,3a,5a,5b,6,9,10,11,12,13,14,16a,16b-十四氢-4,14-二甲基-1H-as-苯并二茚并[3,2-d]氧杂环十二碳六烯-7,15-二酮(也称为“Et-L”)的混合物的通用名。
乙基多杀菌素可以通过Et-J和Et-L的混合物的氢化生成。美国专利号6,011,981提供了使用7摩尔％(mol％)负载量的威尔金森(Wilkinson)催化剂(三(三苯基膦)氯化铑(I)(Rh(PPh3)3Cl))进行的5,6-二氢多杀菌素J(实例F27)的示例性合成。然而，该方法需要高温，且收率需要进一步提高。此外，美国专利号7,683,161提供了用于乙基多杀菌素合成的某些非均相催化剂。然而，该方法需要相对高负载量的催化剂。US 6,011,981和US 7,683,161均据此以引用方式整体并入本文.
因此，仍然需要开发用于以高收率产生乙基多杀菌素的新型有效催化剂。
发明内容
本发明基于以下发现：与先前方法相比，二-μ-氯四乙烯二铑(I)[Rh(C2H4)2Cl]2和/或[Rh(COD)2][BF4]的非均相催化剂可用于通过以较低的催化剂负载量实现较高的收率来产生乙基多杀菌素。此外，也可添加一种或多种磷配体供体，以进一步提高收率/效率。本文提供的催化剂、方法和/或体系使得能够以具有成本效益的方式以相对简单的工序大量产生乙基多杀菌素。
在一个方面，提供了用于产生乙基多杀菌素的方法。该方法包括在存在选自[Rh(C2H4)2Cl]2、[Rh(COD)2][BF4]、[(COD)RhCL]2、[Rh(COD)2][OTs]及其组合的非均相催化剂的情况下，在15℃和100℃之间的温度以及5磅每平方英尺(表压力)(psig)和200psig之间的氢气压力下，使3’-O-乙基多杀菌素J和3’-O-乙基多杀菌素L的混合物氢化。
在一个实施方案中，非均相催化剂选自[Rh(C2H4)2Cl]2、[Rh(COD)2][BF4]及其组合。在另一个实施方案中，该方法还包括添加磷配体供体。在另一个实施方案中，磷配体供体包括三(3,5-二甲基苯基)膦。在另一个实施方案中，磷配体供体选自
在另一个实施方案中，温度在25℃和80℃之间，在25℃和50℃之间；在40℃和70℃之间；或在30℃和65℃之间。在另一个实施方案中，温度为约30℃、45℃或65℃。在另一个实施方案中，氢气压力在50psig和200psig之间；在60psig和150psig之间；在100psig和180psig之间；或在140psig和160psig之间。在另一个实施方案中，氢气压力为约60psig或150psig。在另一个实施方案中，乙基多杀菌素的收率等于约或大于75％、80％、85％、90％或95％。在另一个实施方案中，催化剂负载量在0.01摩尔％和2摩尔％之间；在0.05摩尔％和1摩尔％之间；在0.02摩尔％和0.1摩尔％之间；或在0.1摩尔％和0.5摩尔％之间。
在另一个方面，提供了用于产生乙基多杀菌素的体系，该体系包含选自[Rh(C2H4)2Cl]2、[Rh(COD)2][BF4]、[(COD)RhCL]2、[Rh(COD)2][OTs]及其组合的非均相催化剂。在一个实施方案中，非均相催化剂选自[Rh(C2H4)2Cl]2、[Rh(COD)2][BF4]及其组合。在另一个实施方案中，该体系还包含磷配体供体。在另一个实施方案中，磷配体供体包括三(3,5-二甲基苯基)膦。在另一个实施方案中，磷配体供体选自
在另一个方面，提供了用于产生乙基多杀菌素的方法，其中该方法在15℃和100℃之间的温度以及5psig和200psig之间的氢气压力下使用本文提供的体系。
在另一个实施方案中，温度在25℃和80℃之间；在25℃和50℃之间；在40℃和70℃之间；或在30℃和65℃之间。在另一个实施方案中，温度为约30℃、45℃或65℃。在另一个实施方案中，氢气压力在50psig和200psig之间；在60psig和150psig之间；在100psig和180psig之间；或在140psig和160psig之间。在另一个实施方案中，氢气压力为约60psig或150psig。在另一个实施方案中，乙基多杀菌素的收率等于约或大于75％、80％、85％、90％或95％。在另一个实施方案中，催化剂负载量在0.01摩尔％和2摩尔％之间；在0.05摩尔％和1摩尔％之间；在0.02摩尔％和0.1摩尔％之间；或在0.1摩尔％和0.5摩尔％之间。
具体实施方式
乙基多杀菌素是5,6-二氢-3'-乙氧基多杀菌素J(主要组分)和3'-乙氧基多杀菌素L的混合物。该混合物可以通过多杀菌素J和多杀菌素L的混合物的乙氧基化然后氢化来制备。因此，乙基多杀菌素是半合成多杀菌素和50-90％(2R,3aR,5aR,5bS,9S,13S,14R,16aS,16bR)-2-(6-脱氧-3-O-乙基-2,4-二-O-甲基-α-L-甘露吡喃糖氧基)-13-[(2R,5S,6R)-5-(二甲基氨基)四氢-6-甲基吡喃-2-基氧基]-9-乙基-2,3,3a,4,5,5a,5b,6,9,10,11,12,13,14,16a,16b-十六氢-14-甲基1H-as-苯并二茚并[3,2-d]氧杂环十二碳六烯-7,15-二酮与50-10％(2R,3aR,5aS,5bS,9S,13S,14R,16aS,16bS)-2-(6-脱氧-3-O-乙基-2,4-二-O-甲基-α-L-甘露吡喃糖氧基)-13-[(2R,5S,6R)-5-(二甲基氨基)四氢-6-甲基吡喃-2-基氧基]-9-乙基-2,3,3a,5a,5b,6,9,10,11,12,13,14,16a,16b-十四氢-4,14-二甲基-1H-as-苯并二茚并[3,2-d]氧杂环十二碳六烯-7,15-二酮的混合物。乙基多杀菌素的组分的合成如美国专利No.6,001,981所述。
提供了具有或不具有磷供体配体的基于铑(Rh)的催化剂，诸如[Rh(C2H4)2Cl]2或[Rh(COD)2][BF4]，这些催化剂在Et J/L氢化为乙基多杀菌素之中具有高活性和选择性，并且可用于产生乙基多杀菌素的方法。在一些实施方案中，本文提供的方法和/或体系可以按低于0.1摩尔％的催化剂负载量实现出乎意料高的收率，诸如大于90％。在一些实施方案中，许多此类催化剂体系可使用传统的碳载钯(Pd/C)催化剂的负载量的十分之一提供定量收率的乙基多杀菌素。本文提供的Rh催化剂、方法和体系在所用的催化剂和条件方面不同于先前方法。另外，本文提供的Rh催化剂、方法和体系可以显著低于当前商业负载量的催化剂负载量使用，这将提高方法经济效益。与先前方法相比，本文提供的Rh催化剂、方法和体系的另外优点包括以下中的至少一个：(1)保持选择性；(2)更高的周转数(以TON表示)；以及(3)对起始物料的质量和/或数量相对不敏感。
本文档中引用的所有专利和专利申请据此以引用方式整体并入本文。
本领域内的技术人员将理解，某些变化可基于所提供的公开内容而存在。因此，给出下列实施例以用于阐述本发明，并且不应被解释为限制本发明或权利要求书的范围。
实施例
实施例1
将使用[Rh(C2H4)2Cl]2-[Rh(C2H4)2Cl]2(0.1019克(g)，0.2620毫摩尔(mmol))选择性氢化3’-O-乙基-多杀菌素J/L(Et J/L)的混合物加入10mL容量瓶中，用四氢呋喃(THF)将容量瓶稀释至标线。将催化剂储液搅拌至产生深棕色均相混合物。将储液的等分试样(0.500毫升(mL))加入溶解于异丙醇(IPA；39.5mL)的Et J/L(8.15g Et J，0.0109摩尔(mol)Et J和2.64g Et L，0.00348mol Et L)溶液，搅拌混合物，然后使用气密注射器装入帕尔(Parr)反应器中。将反应器加热至30℃，然后使用氢气加压至60psig。在4.5小时后，排空反应器。通过1H核磁共振(NMR)光谱分析，发现0g Et J(100％转化率)、8.011g 175 Et J(98％收率)和2.64g Et L(100％收率)(TON＝404mol Et J/mol Rh)。
实施例2
将使用[Rh(COD)2][BF4]-[Rh(COD)2][BF4](0.0175g,0.0431mmol)选择性氢化3’-O-乙基-多杀菌素J/L(Et J/L)的混合物溶解于50mL广口瓶中的40mL甲醇中。将纯化的EtJ/L粉末(8.3g,0.0111mol Et J/L)称入50mL容量瓶中，用IPA将容量瓶稀释至标线。一旦EtJ/L溶解，即将黄色催化剂储液的等分试样(0.5mL)与Et J/L储液的等分试样(2.0mL)和IPA(2.5mL)组合。将反应混合物加入Freeslate平行压反应器(PPR)中的玻璃试管。将反应器加热至65℃，并使用氢气加压至150psig。在四小时后，使反应器冷却至室温并排空。通过高效液相色谱(HPLC)分析，发现0.225g Et J(19.9％转化率)和0.0721g Et L(99％收率)(TON＝172mol Et J/mol Rh)。
实施例3
将使用[Rh(COD)2][BF4]和三(3,5-二甲基苯基)膦-[Rh(COD)2][BF4](0.0215g,0.0529mmol)和三(3,5-二甲基苯基)膦(0.0383g,0.1106mmol)(用作磷配体供体)选择性氢化3’-O-乙基-多杀菌素J/L(Et J/L)的混合物称入5mL容量瓶中，用甲醇将容量瓶稀释至标线。将催化剂储液搅拌至产生橙色均相混合物。将催化剂储液的等分试样(0.500mL)加入溶解于IPA(19.5mL)的Et J/L(4.19g Et J,5.62mmol Et J和1.36g Et L,1.79mmol Et L)溶液，搅拌混合物，然后使用气密注射器装入帕尔反应器中。将反应器加热至45℃，然后使用氢气加压至150psig。在八小时后，使反应器冷却至室温并排空。通过1H NMR分析，发现0.124g Et J(97％转化率)和1.32g Et L(98％收率)(TON＝1035mol Et J/mol Rh)。
实施例4
在氮气吹扫的手套箱中，通过在苯或四氢呋喃(THF)中搅拌[Rh(C2H4)Cl]2和磷配体来制备催化剂储液。向6mL玻璃管中装入Et J/L储液进料、Rh催化剂储液、联苯内标和IPA溶剂。将反应混合物加热至65℃，并加压至150psi H2。在四小时后，使反应混合物冷却至室温并排空。使用经校准的1260 Infinity HPLC分析反应混合物，结果如表1所示。

Claims (16)

1.一种用于产生乙基多杀菌素的方法，所述方法包括：
在存在选自[Rh(C2H4)2Cl]2、[Rh(COD)2][BF4]、[(COD)RhCL]2、[Rh(COD)2][OTs]及其组合的非均相催化剂的情况下，在15℃和100℃之间的温度以及5psig和200psig之间的氢气压力下，使3’-O-乙基多杀菌素J和3’-O-乙基多杀菌素L的混合物氢化。
2.根据权利要求1所述的方法，还包括添加磷配体供体。
3.根据权利要求2所述的方法，其中所述磷配体供体包括三(3,5-二甲基苯基)膦。
4.根据权利要求2所述的方法，其中所述磷配体供体选自
5.根据权利要求1所述的方法，其中所述温度为约30℃、45℃或65℃。
6.根据权利要求1所述的方法，其中所述氢气压力为约60psig或150psig。
7.根据权利要求1所述的方法，其中乙基多杀菌素的收率等于约或大于90％。
8.根据权利要求1所述的方法，其中催化剂负载量在0.01摩尔％和2摩尔％之间。
9.根据权利要求1所述的方法，其中所述非均相催化剂选自[Rh(C2H4)2Cl]2、[Rh(COD)2][BF4]及其组合。
10.一种用于产生乙基多杀菌素的体系，所述体系包含选自[Rh(C2H4)2Cl]2、[Rh(COD)2][BF4]、[(COD)RhCL]2、[Rh(COD)2][OTs]及其组合的非均相催化剂。
11.根据权利要求10所述的体系，还包含磷配体供体。
12.根据权利要求11所述的体系，其中所述磷配体供体包括三(3,5-二甲基苯基)膦。
13.根据权利要求11所述的体系，其中所述磷配体供体选自
14.一种用于产生乙基多杀菌素的方法，所述方法包括在15℃和100℃温度以及5psig和200psig的氢气压力下使用根据权利要求10所述的体系。
15.根据权利要求14所述的方法，其中乙基多杀菌素的收率等于约或大于90％。
16.根据权利要求14所述的方法，其中催化剂负载量在0.01摩尔％和2摩尔％之间。
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