CN113336721B - 一种手性n-杂环卡宾催化剂及其制备方法和用途 - Google Patents

一种手性n-杂环卡宾催化剂及其制备方法和用途 Download PDF

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CN113336721B
CN113336721B CN202110721589.4A CN202110721589A CN113336721B CN 113336721 B CN113336721 B CN 113336721B CN 202110721589 A CN202110721589 A CN 202110721589A CN 113336721 B CN113336721 B CN 113336721B
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李俊龙
刘燕青
李青竹
冯鑫
曾荣
邢金盾
戴青松
向朋
邹文林
张翔
寇鑫鑫
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Abstract

本发明公开了一种手性N‑杂环卡宾催化剂及其制备方法和用途，属于有机化学技术领域。本发明手性N‑杂环卡宾催化剂的制备方法具体包括以下步骤：将N‑溴代丁二酰亚胺和对甲苯磺酸加入圆底烧瓶，用DCM溶解后，加入1eq的环庚酮1，室温反应过夜，反应完成后浓缩纯化得到α‑溴代环庚酮2；称取蒙脱土1g，10mmol的对甲基苯胺和40mmol的苯乙炔无溶剂反应，140℃反应8h，冷却至室温，过滤并用乙醚洗涤，收集滤液浓缩纯化得到化合物5，化合物5不对称氢化还原后与α‑溴代环庚酮2进行多步反应合成目标化合物7。本发明可操作性强、合成路线新颖、收率高。本发明能够成功运用于酰胺远端C(sp3)‑H活化串联环化反应，并实现其不对称催化，具有广阔的市场应用前景。

Description

一种手性N-杂环卡宾催化剂及其制备方法和用途
技术领域
本发明涉及一种手性N-杂环卡宾催化剂，具体为一种手性N-杂环卡宾催化剂及其制备方法和用途，属于有机化学应用技术领域。
背景技术
N-杂环卡宾催化剂是一种优势的小分子催化剂，种类繁多，能够高效率的催化多类型反应。由N-杂环卡宾催化剂介导的自由基反应是目前有机化学工作者研究的热点之一，尽管随着研究的不断深入，N-杂环卡宾催化的单电子转移反应类型逐渐增多，但都没有实现反应的不对称化过程。已有的手性N-杂环卡宾催化剂在催化剂活性中间体作为电子给体的自由基反应中兼容性较差，反应活性不高，基本没有适用于该类反应的优势手性N-杂环卡宾催化剂。
如何设计且高收率的制备优势的手性N-杂环卡宾催化剂来实现该类反应的不对称化是目前的研究难点和重点。
发明内容
本发明的目的就在于设计并制备出一种解决上述问题的手性N-杂环卡宾催化剂，本发明提供了一个新的N-杂环卡宾催化剂的制备路线，可操作性强、收率高，并且具有很好的催化活性，得到具有光学活性的催化产物，具有广阔的市场应用前景。
本发明的目的可以通过以下技术方案实现：一种如通式Ⅰ所示的手性N-杂环卡宾催化剂，
Figure BDA0003137024190000021
其中，Ph代表苯基，Me代表甲基。
一种手性N-杂环卡宾催化剂的制备方法，该制备方法具体包括以下步骤：
步骤一：将N-溴代丁二酰亚胺(NBS)和对甲苯磺酸(TsOH)加入圆底烧瓶，用以DCM溶解后加入1eq的环庚酮1，室温反应过夜，反应完成后浓缩纯化得到α-溴代环庚酮2；
步骤二：称取蒙脱土1g，10mmol的对甲基苯胺和40mmol的苯乙炔无溶剂反应，140℃反应8h，反应完成后，冷却至室温，过滤并用乙醚洗涤，收集滤液浓缩纯化得到目标化合物5；
步骤三：在氩气氛围中将0.02eq的[Rh(nbd)2]BF4和0.044eq的DuanPhos在DCM常温配位反应20min；随后加入用少量DCM溶解的化合物5，然后加入MeOH(MeOH/DCM＝10/1)，反应液浓度为0.20M，在80atm的氢气氛围中，30℃反应48h，反应完成后浓缩纯化得到不对称氢化产物6；
步骤四：称取1eq的氢化产物6，加入DMSO(2.0M)溶解，冰浴下加入20N的NaOH(1eq)溶液和1eq的二硫化碳(CS2)，常温反应1h后，在0℃条件下，加入用DMSO(5.0M)溶解的α-溴代环庚酮2，然后室温反应12h，反应完全后用乙酸乙酯和水萃取，收集有机层，干燥浓缩后加入EtOH(2.0M)溶解，再加入0.6eq的HCl回流1h，然后冷却过滤，用水洗涤得白色固体；用冰乙酸(AcOH,0.25M)将的白色固体溶解，在0℃条件下加入3.3eq的H2O2，常温反应1h，浓缩反应液后，加入MeOH(1.5M)溶解，在0℃条件下，逐滴加入MeOH/H2O＝2:1溶解的4.1eq的NaClO4·H2O，然后室温反应30min，过滤后用水进行洗涤，干燥后得到目标手性N-杂环卡宾催化剂7，
制备化合物的技术路线如下所示：
Figure BDA0003137024190000031
上述反应路线中关键中间产物及目标化合物的1H NMR、13C NMR表征：
α-溴代环庚酮
Figure BDA0003137024190000032
淡黄色油状物，产率98％
1H NMR(600MHz,CDCl3)δ4.33(dd,J＝9.6Hz,4.8Hz 1H),2.82–2.78(m,1H),2.46–2.41(m,1H),2.34–2.29(m,1H),1.99–1.92(m,2H),1.92–1.86(m,1H),1.74–1.69(m,1H),1.55–1.48(m,2H),1.37–1.30(m,1H).
13C NMR(150MHz,CDCl3)δ206.1,53.7,39.3,34.1,29.4,26.8,24.8.
4-甲基-2,6-二(1-苯乙烯基)苯胺
Figure BDA0003137024190000041
白色固体，产率66％
1H NMR(600MHz,CDCl3)δ7.39(d,J＝7.2Hz,4H),7.31(t,J＝8.4Hz,4H),7.29–7.27(m,2H),6.95(s,2H),5.80(s,2H),5.38(s,2H),3.39(s,2H),2.29(s,3H).
13C NMR(150MHz,CDCl3)δ147.3,139.6,139.0,130.8,128.5,128.0,127.7,126.7,126.5,116.1,20.3.
4-甲基-2,6-二((R)-1-苯基乙基)苯胺
Figure BDA0003137024190000042
无色油状物，产率95％
1H NMR(600MHz,CDCl3)δ7.25(t,J＝7.2Hz,4H),7.18–7.15(m,6H),7.07(s,2H),3.99(q,J＝7.2Hz,2H),3.22(s,2H),2.38(s,3H),1.59(d,J＝6.6Hz,6H).
13C NMR(150MHz,CDCl3)δ145.9,139.6,129.9,128.6,127.3,126.7,126.2,126.0,40.3,22.3,21.2.
3-(4-甲基-2,6-二((R)-1-苯基乙基)苯基)-噻唑并[d]环庚烷的高氯酸盐
Figure BDA0003137024190000051
白色固体，产率64％
1H NMR(600MHz,CDCl3)δ8.70(s,1H),7.53(s,1H),7.43(s,1H),7.22–7.18(m,3H),7.14–7.13(m,3H),6.74–6.70(m,2H),6.66–6.63(m,2H),3.83(q,J＝7.2Hz,1H),3.33(q,J＝7.2Hz,1H),3.00(dd,J＝15.0Hz,7.2Hz,1H),2.64(dd,J＝15.0Hz,9.0Hz,1H),2.62(s,3H),1.97–1.90(m,2H),1.86–1.81(m,1H),1.68-1.57(m,1H),1.55(d,J＝7.2Hz,6H),1.45–1.38(m,1H),1.27–1.20(m,1H),1.19–1.15(m,1H),0.98–0.91(m,1H).
13C NMR(150MHz,CDCl3)δ156.3,148.1,144.3,143.7,142.4,141.7,140.2,138.6,132.6,129.4,128.7,128.0,127.6,127.3,127.1,126.9,126.0,40.6,39.9,30.6,28.0,26.6,26.4,25.0,22.9,22.1,22.1.
一种手性N-杂环卡宾催化剂在N-杂环卡宾催化剂介导的有机化反应中的用途。
本发明的进一步技术改进在于：所述反应是N-杂环卡宾催化剂介导的自由基历程反应。
本发明的进一步技术改进在于：所述反应是N-杂环卡宾催化剂介导的不对称化反应。
与现有技术相比，本发明的有益效果是：本发明提供了一个新型的N-杂环卡宾催化剂的制备，可操作性强、收率高，并且具有很好的催化活性，得到具有光学活性的催化产物，具有广阔的市场应用前景。
附图说明
下面结合附图和试验例对本发明进一步说明。
图1试验例1消旋体催化产物10的液相谱图。
图2试验例1手性催化产物10的液相谱图。
图3试验例2消旋体催化产物12的液相谱图。
图4试验例2手性催化产物12的液相谱图。
具体实施方式
下面将结合试验例对本发明的技术方案进行清楚、完整地描述，显然，所描述的试验例仅仅是本发明一部分试验例，而不是全部的试验例。基于本发明中的试验例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其它试验例，都属于本发明保护的范围。
试验例1、酰胺远端C(sp3)-H活化串联环化反应
用本发明的N-杂环卡宾催化剂来活化对溴苯甲醛，与酰胺底物8发生反应，能成功的获得酰胺远端C(sp3)-H活化串联环化产物10，通过对反应所用到的碱和溶剂的筛选，以K2CO3作碱，在乙腈中反应时，能以81％的收率得到产物10，其dr值为10:1，er值为75:25。
Figure BDA0003137024190000061
Figure BDA0003137024190000062
Figure BDA0003137024190000071
试验操作：称取N-杂环卡宾催化剂7(0.1eq)，酰胺底物8(1.0eq)，对溴苯甲醛(2.0eq)和碱(1.5eq)于封管内，换气处理三次，加入反应溶剂后60℃反应12h。反应结束后，用二溴甲烷为内标通过1H NMR进行收率和dr值测定，er值通过手性HPLC测定。
催化产物10的1H NMR、13C NMR表征：
Figure BDA0003137024190000072
白色固体
1H NMR(600MHz,CDCl3)δ8.03(d,J＝7.8Hz,1H),7.54–7.41(m,3H),7.39–7.32(m,3H),7.23(d,J＝7.2Hz,1H),3.43(q,J＝6.6Hz,1H),3.41(s,1H),2.84(s,3H),1.23(d,J＝7.2Hz,3H).
13C NMR(150MHz,CDCl3)δ(ppm)δ165.0,140.7,138.6,132.6,131.7,128.3,128.2,127.8,127.4,126.0,122.4,90.5,44.1,30.2,13.8.
试验结果表明，本发明催化剂具有优异的催化活性，不仅能以良好的收率得到催化产物，还能实现中等的对映选择性和良好的非对映选择性控制。
试验例2、烯烃的双酰基化反应
用本发明的N-杂环卡宾催化剂来活化对溴苯甲醛，在氧化条件下，与另一分子苯甲醛和苯乙烯反应，成功得到烯烃的双功能团化产物，通过对反应所用到的碱和溶剂的筛选，以Cs2CO3作碱，在三氟甲苯中反应时，能以70％的收率得到产物12，er值为68:32。
Figure BDA0003137024190000081
Figure BDA0003137024190000082
试验操作：称取N-杂环卡宾催化剂7(0.1eq)，对溴苯甲醛(3.0eq)，氧化剂(1.5eq)于封管内，换气处理三次，加入反应溶剂后加入碱(1.5eq)和苯乙烯(1.0eq),然后室温反应12h。反应结束后，分离纯化得到目标产物，er值通过手性HPLC测定。
催化产物12的1H NMR、13C NMR表征：
Figure BDA0003137024190000083
白色固体
1H NMR(600MHz,CDCl3)δ7.82(d,J＝9.0Hz,2H),7.78(d,J＝8.4Hz,2H),7.54(d,J＝9.0Hz,2H),7.49(d,J＝8.4Hz,2H),7.28–7.25(m,4H),7.22–7.18(m,1H),5.17(dd,J＝10.2Hz,3.6Hz,1H),4.10(dd,J＝18.0Hz,9.6Hz,1H),3.19(dd,J＝18.0Hz,3.6Hz,1H).
13C NMR(150MHz,CDCl3)δ(ppm)δ197.8,197.0,138.0,135.0,131.9,131.8,130.4，129.7,129.3,128.6,128.2,128.1,127.6,48.8,43.7.
试验结果表明，本发明催化剂能优异的催化不同类型的自由基反应。
综上所述，本发明N-杂环卡宾催化剂的制备可操作性强、收率高，并且具有很好的催化活性，得到具有光学活性的催化产物，具有广阔的市场应用前景。
除特别标注外，本发明所用试剂和测试设备均为常规的市售试剂和设备
以上公开的本发明优选试验例只是用于帮助阐述本发明。优选试验例并没有详尽叙述所有的细节，也不限制该发明仅为的具体实施方式。显然，根据本说明书的内容，可作很多的修改和变化。本说明书选取并具体描述这些试验例，是为了更好地解释本发明的原理和实际应用，从而使所属技术领域技术人员能很好地理解和利用本发明。本发明仅受权利要求书及其全部范围和等效物的限制。

Claims (4)

1.一种如通式Ⅰ所示的手性N-杂环卡宾催化剂，其特征在于：
Figure FDA0003232817680000011
其中，Ph代表苯基，Me代表甲基；
所述手性N-杂环卡宾催化剂的制备方法具体包括以下步骤：
步骤一：将1，N-溴代丁二酰亚胺和对甲苯磺酸加入圆底烧瓶，用以DCM溶解后加入1eq的环庚酮，室温反应过夜，反应完成后浓缩纯化得到α-溴代环庚酮2；
步骤二：称取蒙脱土1g，10mmol的对甲基苯胺和40mmol的苯乙炔无溶剂反应，140℃反应8h，反应完成后，冷却至室温，过滤并用乙醚洗涤，收集滤液浓缩纯化得到目标化合物5；
步骤三：在氩气氛围中将0.02eq的[Rh(nbd)2]BF4和0.044eq的DuanPhos在DCM常温配位反应20min；随后加入用少量DCM溶解的化合物5，然后加入DCM 10 倍 量的MeOH，反应液浓度为0.20M，在80atm的氢气氛围中，30℃反应48h，反应完成后浓缩纯化得到不对称氢化产物6；
步骤四：称取1eq的氢化产物6，加入2.0M 的DMSO溶解，冰浴下加入1eq 的20N的NaOH溶液和1eq的二硫化碳，常温反应1h后，在0℃条件下，加入用5.0M 的DMSO溶解的α-溴代环庚酮2，然后室温反应12h，反应完全后用乙酸乙酯和水萃取，收集有机层，干燥浓缩后加入2.0M 的EtOH溶解，再加入0.6eq的HCl回流1h，然后冷却过滤，用水洗涤得白色固体；用0.25M 的冰乙酸将白色固体溶解，在0℃条件下加入3.3eq的H2O2，常温反应1h，浓缩反应液后，加入1.5M 的MeOH溶解，在0℃条件下，逐滴加入MeOH/H2O＝2:1溶解的4.1eq的NaClO4·H2O，然后室温反应30min，过滤后用水进行洗涤，干燥后得到目标手性N-杂环卡宾催化剂7，
制备化合物的技术路线如下所示：
Figure FDA0003232817680000021
2.如权利要求1所述的一种手性N-杂环卡宾催化剂在N-杂环卡宾催化剂介导的有机反应中的应用 。
3.根据权利要求2所述的一种手性N-杂环卡宾催化剂在N-杂环卡宾催化剂介导的有机反应中的应用 ，其特征在于：所述反应是N-杂环卡宾催化剂介导的自由基历程反应。
4.根据权利要求2所述的一种手性N-杂环卡宾催化剂在N-杂环卡宾催化剂介导的有机反应中的应用 ，所述反应是N-杂环卡宾催化剂介导的不对称化反应。
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