CN109336896A - 轴手性双齿配体及其在铜催化的偶联反应 - Google Patents

轴手性双齿配体及其在铜催化的偶联反应 Download PDF

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CN109336896A
CN109336896A CN201811165693.4A CN201811165693A CN109336896A CN 109336896 A CN109336896 A CN 109336896A CN 201811165693 A CN201811165693 A CN 201811165693A CN 109336896 A CN109336896 A CN 109336896A
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许萌
柯军梁
王哲
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Shangyu Research Institute of ZJUT
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Abstract

本发明公开了一种轴手性双齿配体及其在铜催化的偶联反应。轴手性双齿配体，结构式如下：

Description

轴手性双齿配体及其在铜催化的偶联反应
技术领域
本发明属于金属催化领域，具体涉及一种轴手性双齿配体及其在Nozaki-Hiyama-Kishi脱羧C-C偶联反应中的应用。
背景技术
最近几年，金属钯催化的脱羧偶联反应，得到了越来越多的关注，取得了较大的研究进步，尤其是在二芳基化合物的合成中取得了较大的突破，例如，德国的巴斯夫公司采用二芳基化合物合成技术，发现了一种新药，对真菌有很好的抑制作用。
Goossen等报道了，钯催化2-硝基苯甲酸脱羧与溴苯偶联，制备二芳基化合物的相关研究，该研究提供了一种脱羧制备联苯类化合物的方法，是巴斯德公司制备新药医药中间体的关键合成步骤，反应步骤如下：
Liu开发了一类钯金属催化的芳香羧酸类化合物与苯硼酸的脱羧C-C偶联反应，拓展了反应的底物，扩大了反应的适用范围，反应步骤如下：
经过长时间的科研探索，科研工作者已经逐步解决了之前联芳基化合物的合成需要采用有机锡试剂、有机锌试剂、格式试剂和其他有机金属试剂的限制，减少了重金属对环境的危害，但是仍然存在着一定的局限性，一般催化剂需要钯等贵金属催化剂，合成成本相对较高，这些制约了该反应的大规模应用。
发明内容
本发明的目的是提供一种轴手性双齿配体，同时提供其在铜催化的偶联反应，解决如何在温和的条件下取得了较高的收率技术问题。
轴手性双齿配体，结构式如下：其中R为2-Me或者3-Ome或者2-t-Bu或者2-F或者2,3,4-F。
轴手性双齿配体在铜催化的偶联反应，包括如下步骤：将配体与铜盐在乙醚中搅拌配位，浓缩旋干，得到催化剂；在10mL单口反应瓶中加入三甲氧基苯基硅、溴苯，加入乙醇溶解，然后加入碱，加入5mol％的上述催化剂，将反应升高至60-100℃,反应6-12h,反应结束后直接过柱，得到白色固体产物。
所述碱为KOH或NaOH或K2CO3。
所述铜盐为CuI或CuCl或CuBr或Cu(OAc)2。
所述偶联反应为应用于Nozaki-Hiyama-Kishi脱羧C-C偶联反应。
本发明的有益效果是：采用结构新颖的轴手性双齿化合物即轴手性双齿配体作为配体与廉价金属铜进行配位，所得催化剂活性较高，价格便宜，制备简单，反应条件温和，无需除水除氧，利用大规模应用。
具体实施方式
实施例1
在10mL单口反应瓶中加入50mg三甲氧基苯基硅，45mg溴苯，加入2mL乙醇溶解，然后加入35mg KOH，加入5mol％的CuCl和A1配合后的催化剂，将反应升高至100℃,反应6h,反应结束后直接过柱，得到白色固体产物,收率为56％。
实施例2
在10mL单口反应瓶中加入50mg三甲氧基苯基硅，45mg溴苯，加入2mL乙醇溶解，然后加入35mg KOH，加入5mol％的CuCl和A1配合后的催化剂，将反应升高至100℃,反应12h,反应结束后直接过柱，得到白色固体产物,收率为81％。
实施例3
在10mL单口反应瓶中加入50mg三甲氧基苯基硅，45mg溴苯，加入2mL乙醇溶解，然后加入35mg KOH，加入5mol％的CuBr和A1配合后的催化剂，将反应升高至100℃,反应12h,反应结束后直接过柱，得到白色固体产物,收率为86％。
实施例4
在10mL单口反应瓶中加入50mg三甲氧基苯基硅，45mg溴苯，加入2mL乙醇溶解，然后加入35mg KOH，加入5mol％的CuI和A1配合后的催化剂，将反应升高至100℃,反应12h,反应结束后直接过柱，得到白色固体产物,收率为92％。
实施例5
在10mL单口反应瓶中加入50mg三甲氧基苯基硅，45mg溴苯，加入2mL乙醇溶解，然后加入35mg KOH，加入5mol％的Cu(OAc)2和A1配合后的催化剂，将反应升高至100℃，反应12h，反应结束后直接过柱，得到白色固体产物，收率为89％。
实施例6
在10mL单口反应瓶中加入55mg三甲氧基苯基硅，50mg对甲氧基溴苯，加入2mL乙醇溶解，然后加入35mg NaOH，加入5mol％的CuI和A2配合后的催化剂,将反应升高至100℃,反应9h,反应结束后直接过柱，得到白色固体产物,收率为87％。
实施例7
在10mL单口反应瓶中加入55mg三甲氧基苯基硅，50mg间硝基溴苯，加入2mL甲醇溶解，然后加入35mg KOH，加入5mol％的CuI和A3配合后的催化剂,将反应升高至80℃,反应6h,反应结束后直接过柱，得到浅黄色固体产物,收率为94％。
实施例8
在10mL单口反应瓶中加入55mg三甲氧基苯基硅，50mg邻硝基溴苯，加入2mL乙醇溶解，然后加入35mg NaOH，加入5mol％的CuI和A4配合后的催化剂,将反应升高至100℃,反应12h,反应结束后直接过柱，得到浅黄色固体产物,收率为89％。
实施例9
在10mL单口反应瓶中加入58mg三甲氧基苯基硅，50mg对硝基溴苯，加入2mL乙醇溶解，然后加入35mg KOH，加入5mol％的CuI和A5配合后的催化剂,将反应升高至90℃,反应7h,反应结束后直接过柱，得到浅黄色固体产物,收率为96％。
实施例10
在10mL单口反应瓶中加入55mg三甲氧基苯基硅，50mg间溴吡啶，加入2mL乙醇溶解，然后加入35mg KOH，加入5mol％的CuCl和A1配合后的催化剂,将反应升高至100℃,反应12h,反应结束后直接过柱，得到白色固体产物,收率为81％。

Claims (5)

1.轴手性双齿配体，其特征在于：结构式如下：其中R为2-Me或者3-Ome或者2-t-Bu或者2-F或者2,3,4-F。
2.轴手性双齿配体在铜催化的偶联反应，其特征在于：包括如下步骤：将配体与铜盐在乙醚中搅拌配位，浓缩旋干，得到催化剂；在10mL单口反应瓶中加入三甲氧基苯基硅、溴苯，加入乙醇溶解，然后加入碱，加入5mol％的上述催化剂，将反应升高至60-100℃,反应6-12h,反应结束后直接过柱，得到白色固体产物。
3.根据权利要求2中所述的轴手性双齿配体在铜催化的偶联反应，其特征在于：所述碱为KOH或NaOH或K2CO3。
4.根据权利要求2中所述的轴手性双齿配体在铜催化的偶联反应，其特征在于：所述铜盐为CuI或CuCl或CuBr或Cu(OAc)2。
5.根据权利要求2中所述的轴手性双齿配体在铜催化的偶联反应，其特征在于：所述偶联反应为应用于Nozaki-Hiyama-Kishi脱羧C-C偶联反应。
CN201811165693.4A 2018-10-08 2018-10-08 轴手性双齿配体及其在铜催化的偶联反应 Pending CN109336896A (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110105378A (zh) * 2019-05-27 2019-08-09 华中科技大学 一种铜基圆偏振发光材料及其制备与应用
CN111499648A (zh) * 2020-04-27 2020-08-07 江苏医药职业学院 一种轴手性双齿配体、催化剂及其制备方法和应用

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110105378A (zh) * 2019-05-27 2019-08-09 华中科技大学 一种铜基圆偏振发光材料及其制备与应用
CN111499648A (zh) * 2020-04-27 2020-08-07 江苏医药职业学院 一种轴手性双齿配体、催化剂及其制备方法和应用

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Application publication date: 20190215

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