CN101143818A - Pd-催化的烯丙基取代反应中的对映选择性反转的方法 - Google Patents

Pd-催化的烯丙基取代反应中的对映选择性反转的方法 Download PDF

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CN101143818A
CN101143818A CNA2007100464576A CN200710046457A CN101143818A CN 101143818 A CN101143818 A CN 101143818A CN A2007100464576 A CNA2007100464576 A CN A2007100464576A CN 200710046457 A CN200710046457 A CN 200710046457A CN 101143818 A CN101143818 A CN 101143818A
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张万斌
谢芳
刘德龙
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Shanghai Jiaotong University
Nippon Chemical Industrial Co Ltd
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Abstract

一种化工技术领域的Pd－催化的烯丙基取代反应中的对映选择性反转的方法，方法如下：将相同手性骨架的茂金属双膦配体应用于Pd－催化的1，3－二苯基烯丙基醋酸酯的不对称烯丙基取代反应中，所用的亲核试剂是丙二酸二甲酯或苄胺。当二苯基膦的邻位上的基团为酯基时，催化得到S构型的产物。若还原成羟甲基时，则诱导出R构型的产物，将羟基醚化或酯化具有同样的诱导作用。该方法操作简便，便于预测产物的立体构型，可筛选的范围广。

Description

Pd-催化的烯丙基取代反应中的对映选择性反转的方法
技术领域
本发明涉及一种化工技术领域的的方法，具体涉及一种Pd-催化的烯丙基取代反应中的对映选择性反转的方法。
背景技术
在不对称催化反应中配体的立体因素对产物的绝对构型及对映选择性的大小有着很大的影响。要分别得到两种不同构型的产物，常用的方法是合成两种构型相反的配体。由于自然界本身的不对称性，往往一种构型的手性源很充足，但另一种构型却很难得到，从而使得这一方法的应用具有很大的局限性。因此，化学家们一直在致力于在原有配体的构型(手性骨架)不变的情况下，通过改变其它的因素而达到对映选择性反转的研究。其中通过对原有手性配体进行简单的结构修饰是比较有意义的方法之一，其操作简便，便于预测产物的立体构型，可筛选的范围广。
经对现有技术的文献检索发现，Moberg等人在J.Org.Chem.(有机化学)2005年第70卷第9882-9891页发表的Conformational Preferences andEnantiodiscrimination of Phosphino-4-(1-hydroxyalkyl)oxazoline-Metal-Olefin Complexes Resulting from an OH-Metal Hydrogen Bond(膦噁唑啉金属和烯烃络合物中金属-羟基键中氢键导致的构象优先和对映识别的研究)，该文中提出在4位含羟基的噁唑啉环上的中心手性可诱导出S构型的产物。若将羟基保护则可能得到R构型的产物。其不足在于：产物的构型预测性较差，ee值较低，甚至得到外消旋的产物。
发明内容
本发明的目的在于针对现有技术的不足，提供一种将相同手性骨架面手性双膦配体用于Pd-催化的烯丙基取代反应中的对映选择性反转的方法。本发明产物的构型预测性较好，操作简便。
本发明是通过以下技术方案实现的，本发明将相同手性骨架不同邻位取代的茂金属双膦配体应用于Pd-催化的1，3-二苯基烯丙基醋酸酯的不对称烯丙基取代反应中，具体为：将手性配体与二聚烯丙基氯化钯于溶剂中反应，然后，依次加入1，3-二苯基烯丙基醋酸酯和亲核试剂反应。
所述手性配体的二苯基膦邻位取代基上R基团为烷基或含酰胺的基团时，得到的产物的立体构型为S，将环茂二烯环上的酯基还原为烃甲基得到(S)-(S)-1，1’-二(二苯基膦)-2，2’-二甲氧基羰基甲基茂金属，则诱导出R构型的产物，进而将羟基进行醚化得到(S)-(S)-1，1‘-二(二苯基膦基)-2，2’-二(甲氧基甲基)茂金属或酯化得到(S)-(S)-1，1’-二(二苯基膦)-2，2’-二(乙酰氧基甲基)茂金属，均得到R构型的产物，配体中茂金属是二茂铁或二茂钌。
所述手性配体的用量为钯的用量的1.2倍。
所用的溶剂可以是二氯甲烷、乙晴、四氢呋喃、1，2-二氯乙烷、N，N’-二甲基甲酰胺、乙醚或甲苯。
所述亲核试剂为丙二酸二甲酯或苄胺，其中烷基化反应中所用的亲核试剂是丙二酸二甲酯，胺基化反应中所用的亲核试剂是苄胺。
所述亲核试剂的用量为1，3-二苯基烯丙基醋酸酯的2～3倍。
所述烷基化反应中还需加入N，O-二(三甲基硅基)-乙酰胺(BSA)和醋酸钠。BSA的用量与丙二酸二甲酯的用量相等，醋酸钠的用量为催化量。
所述反应，其温度为室温到-78℃。
本发明上述反应路线如下：
Figure A20071004645700041
式中：R＝甲基、乙基等1～4碳的烷基或含酰胺官能团的基团；M可以是铁原子或钌原子。
本发明可用自然界资源丰富但单一手性的化合物为原料，合成出的相同手性骨架但不同取代的配体，这些配体可分别诱导出不同构型的产物。本发明操作简便，便于预测产物的立体构型，可筛选的范围广，ee值可达86.2％。
具体实施方式
下面对本发明的实施例作详细说明：本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的操作过程，但本发明的保护范围不限于下述的实施例。
实施例一
烷基化反应
在氮气氛下，手性配体(0.03mmol)和[Pd(η3-C3H5)Cl]2(4.60mg，12.5μmol)溶于干燥的乙腈(1mL)中于在室温下搅拌1h。所得原位催化剂用注射器加入到另一份溶液中，该溶液是由1，3-二苯基烯丙基醋酸酯(0.252g，1.00mmol)和无水醋酸钾(0.0020g，20μmol)溶于干燥的乙腈(2mL)形成。然后，依次加入丙二酸二甲酯(0.396g，3.00mmol)和BSA(0.613g，3.00mmol)，TLC监控反应，0.5h反应结束。以乙醚冲稀体系(20mL)，分别以冷的饱和NH4Cl水溶液(25mL)、水和饱和食盐水洗，无水Na2SO4干燥，减压蒸除溶剂。残余物柱层析(乙酸乙酯/石油醚＝1/8)得产物。手性OD-H柱上测ee值：7.6～45.3％
1H NMR(400MHz，CDCl3)：δ3.51(s，3H)，3.69(s，3H)，3.94(d，J＝10.8Hz，1H)，4.25(dd，J＝8.8，10.8Hz，1H)，6.32(dd，J＝8.4，15.6Hz，1H)，6.46(d，J＝15.6Hz，1H)，7.17-7.32(m，10H)。
实施例二
烷基化反应
在氮气氛下，手性配体(0.03mmol)和[Pd(η3-C3H5)Cl]2(4.60mg，12.5μmol)溶于干燥的二氯甲烷(1mL)中于在室温下搅拌1h。所得原位催化剂用注射器加入到另一份溶液中，该溶液是由1，3-二苯基烯丙基醋酸酯(0.252g，1.00mmol)和无水醋酸钾(0.0020g，20μmol)溶于干燥的二氯甲烷(2mL)形成。降温到-78℃，然后，依次加入丙二酸二甲酯(0.396g，3.00mmol)和BSA(0.613g，3.00mmol)，TLC监控反应结束。以乙醚冲稀体系(20mL)，分别以冷的饱和NH4Cl水溶液(25mL)、水和饱和食盐水洗，无水Na2SO4干燥，减压蒸除溶剂。残余物柱层析(乙酸乙酯/石油醚＝1/8)得产物。手性OD-H柱上测ee值：72.9％
1H NMR(400MHz，CDCl3)：δ3.51(s，3H)，3.69(s，3H)，3.94(d，J＝10.8Hz，1H)，4.25(dd，J＝8.8，10.8Hz，1H)，6.32(dd，J＝8.4，15.6Hz，1H)，6.46(d，J＝15.6Hz，1H)，7.17-7.32(m，10H)。
实施例三
胺基化反应
在氮气氛下，手性配体(0.015mmol)和[Pd(η3-C3H5)Cl]2(2.3mg，0.0063mmol)溶于干燥的甲苯(1mL)中于在室温下搅拌1h，制得原位催化剂。向其中加入由1，3-二苯基烯丙基醋酸酯(126mg，0.5mmol)和干燥的甲苯(1mL)形成的溶液。待10min后加入苄胺(131μL，1.5mmol)，TLC监控反应，20min反应结束。以乙醚冲稀体系(20mL)，分别以冷的饱和NH4Cl水溶液(25mL)、水和饱和食盐水洗，无水Na2SO4干燥，减压蒸除溶剂。残余物柱层析(乙酸乙酯/石油醚＝1/10)得产物。手性OJ-H柱测ee值：63.1～70.1％。
1H NMR(400MHz，CDCl3)：δ3.75-3.81(m，2H)，4.41(d，J＝7.6Hz，1H)，6.32(dd，J＝7.6，15.6Hz，1H)，6.58(d，J＝16Hz，1H)，7.21-7.44(m，15H)。
实施例四
胺基化反应
在氮气氛下，手性配体(0.015mmol)和[Pd(η3-C3H5)Cl]2(2.3mg，0.0063mmol)溶于干燥的四氢呋喃(1mL)中于在室温下搅拌1h，制得原位催化剂。向其中加入由1，3-二苯基烯丙基醋酸酯(126mg，0.5mmo1)和干燥的四氢呋喃(1mL)形成的溶液。降温到-10℃，待10min后加入苄胺(131μL，1.5mmol)，TLC监控反应，20min反应结束。以乙醚冲稀体系(20mL)，分别以冷的饱和NH4Cl水溶液(25mL)、水和饱和食盐水洗，无水Na2SO4干燥，减压蒸除溶剂。残余物柱层析(乙酸乙酯/石油醚＝1/10)得产物。手性OJ-H柱测ee值：86.2％。
1H NMR(400MHz，CDCl3)：δ3.75-3.81(m，2H)，4.41(d，J＝7.6Hz，1H)，6.32(dd，J＝7.6，15.6Hz，1H)，6.58(d，J＝16Hz，1H)，7.21-7.44(m，15H)。

Claims (8)

1.一种Pd-催化的烯丙基取代反应中的对映选择性反转的方法，其特征是，将手性配体与二聚烯丙基氯化钯于溶剂中反应，然后，依次加入1，3-二苯基烯丙基醋酸酯和亲核试剂反应。
2.根据权利要求1所述的Pd-催化的烯丙基取代反应中的对映选择性反转的方法，其特征是：所述手性配体的二苯基膦邻位取代基上R基团为烷基或含酰胺的基团时，得到的产物的立体构型为S，将环茂二烯环上的酯基还原为烃甲基得到(S)-(S)-1，1’-二(二苯基膦)-2，2’-二甲氧基羰基甲基茂金属，则诱导出R构型的产物，进而将羟基进行醚化得到(S)-(S)-1，1‘-二(二苯基膦基)-2，2’-二(甲氧基甲基)茂金属或酯化得到(S)-(S)-1，1’-二(二苯基膦)-2，2’-二(乙酰氧基甲基)茂金属，均得到R构型的产物，配体中茂金属是二茂铁或二茂钌。
3.根据权利要求1所述的Pd-催化的烯丙基取代反应中的对映选择性反转的方法，其特征是：所述亲核试剂是丙二酸二甲酯或苄胺，其中烷基化反应中所用的亲核试剂是丙二酸二甲酯，胺基化反应中所用的亲核试剂是苄胺。
4.根据权利要求1或3所述的Pd-催化的烯丙基取代反应中的对映选择性反转的方法，其特征是：所述亲核试剂的用量为1，3-二苯基烯丙基醋酸酯的2～3倍。
5.根据权利要求3所述的Pd-催化的烯丙基取代反应中的对映选择性反转的方法，其特征是：所述烷基化反应中在加入丙二酸二甲酯后加入N，O-二(三甲基硅基)-乙酰胺和醋酸钠。
6.根据权利要求5所述的Pd-催化的烯丙基取代反应中的对映选择性反转的方法，其特征是：所述N，O-二(三甲基硅基)-乙酰胺的用量与丙二酸二甲酯的用量相等，醋酸钠的用量为催化量。
7.根据权利要求1所述的Pd-催化的烯丙基取代反应中的对映选择性反转的方法，其特征是：所述反应，其温度为室温到-78℃。
8.根据权利要求1或2所述的Pd-催化的烯丙基取代反应中的对映选择性反转的方法，其特征是：所述手性配体的用量为钯的用量的1.2倍。
CNA2007100464576A 2007-09-27 2007-09-27 Pd-催化的烯丙基取代反应中的对映选择性反转的方法 Pending CN101143818A (zh)

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PCT/CN2008/072561 WO2009043303A1 (fr) 2007-09-27 2008-09-27 Procédé de stéréosélectivité dans une réaction de substitution allylique par catalyse au palladium
CN200880108610A CN101808975A (zh) 2007-09-27 2008-09-27 由Pd-催化的烯丙基取代反应的立体选择性制造方法

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CN107074675A (zh) * 2015-01-30 2017-08-18 四川海思科制药有限公司 一种手性的2‑[1‑环丙基乙基]‑6‑异丙基‑苯酚的制备方法
CN113980053A (zh) * 2021-11-08 2022-01-28 百色学院 手性硫醚-膦化合物及其制备方法
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CN102452911B (zh) * 2010-10-22 2014-08-27 上海交通大学 基于钯催化的烯丙基取代反应实现c-n键转变c-c键的方法
CN107074675A (zh) * 2015-01-30 2017-08-18 四川海思科制药有限公司 一种手性的2‑[1‑环丙基乙基]‑6‑异丙基‑苯酚的制备方法
CN107074675B (zh) * 2015-01-30 2019-12-20 四川海思科制药有限公司 一种手性的2-[1-环丙基乙基]-6-异丙基-苯酚的制备方法
CN113980053A (zh) * 2021-11-08 2022-01-28 百色学院 手性硫醚-膦化合物及其制备方法
CN113980053B (zh) * 2021-11-08 2023-11-03 百色学院 手性硫醚-膦化合物及其制备方法
CN115057885A (zh) * 2022-06-23 2022-09-16 上海交通大学 一种苯乙烯轴手性膦配体及其合成方法与应用
CN115057885B (zh) * 2022-06-23 2023-10-17 上海交通大学 一种苯乙烯轴手性膦配体及其合成方法与应用

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