CN113387876A - 一种镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法及产物 - Google Patents

一种镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法及产物 Download PDF

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CN113387876A
CN113387876A CN202110827240.9A CN202110827240A CN113387876A CN 113387876 A CN113387876 A CN 113387876A CN 202110827240 A CN202110827240 A CN 202110827240A CN 113387876 A CN113387876 A CN 113387876A
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沈志良
褚雪强
崔艳影
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Nanjing Tech University
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Abstract

本发明公开了一种镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法及产物，包括，在氮气氛围下，加热镁屑与氯化锂的混合物；待混合物降至室温，向其中加入超干溶剂；随后分别加入鏻盐化合物、催化剂、配体和芳基溴化物，搅拌反应；将反应产物淬灭、洗涤、萃取和干燥，再通过柱层析分离得芳基化吡啶或二嗪化合物。本发明制备方法反应条件温和，具有后处理简单、步骤绿色、污染低、经济效益高等特点。

Description

一种镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法及 产物
技术领域
本发明属于有机化合物合成技术领域，具体涉及到一种镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法及产物。
背景技术
含有吡啶或二嗪部分的有机分子广泛存在于药物、农用化学品、材料、配体和天然产物中。因此，开发用于构建吡啶和二嗪类杂环化合物的有效方法受到广泛关注。在这方面，McNally研究实验室最近所做的努力开创性地表明，通过吡啶或二嗪与三芳基膦的反应可以很容易地获得吡啶基或二嗪基鏻盐，可以作为多功能亲电试剂进行广泛的有机转化(例如卤化、烷氧基化、氘化、氟烷基化和胺化)，生成吡啶和二嗪的杂环化合物。例如，在2017年和2019年，McNally及其同事分别报道了在镍或钴催化剂存在下，吡啶鏻盐与芳基硼酸或烷基锌试剂的Suzuki型和Negishi型交叉偶联。我们设想，如果吡啶鏻盐可以直接与有机卤化物交叉偶联，而无需使用预先合成的有机金属化合物，则可以显着提高反应效率。
近几十年来，通过直接使用两种不同的亲电有机卤化物作为底物的还原交叉偶联反应已被证明是形成碳-碳键的直接方法。沿着这条路线，在2020年，Feng和同事报道在催化量的钯催化剂RuPhos和高氯酸银存在下，吡啶鏻盐与芳基碘的直接交叉偶联。然而，在他们的报道中，使用了相对更昂贵的钯催化剂和银盐。此外，该反应仅适用于更昂贵的芳基碘化物。因此，开发使用较便宜的催化剂/添加剂和芳基溴的替代方法仍然是非常需要的。
发明内容
本部分的目的在于概述本发明的实施例的一些方面以及简要介绍一些较佳实施例。在本部分以及本申请的说明书摘要和发明名称中可能会做些简化或省略以避免使本部分、说明书摘要和发明名称的目的模糊，而这种简化或省略不能用于限制本发明的范围。
鉴于上述和/或现有技术中存在的问题，提出了本发明。
为解决上述技术问题，本发明提供了如下技术方案：一种镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法，包括，
在氮气氛围下，加热镁屑与氯化锂的混合物；
待混合物降至室温，向其中加入超干溶剂；随后分别加入鏻盐化合物、催化剂、配体和芳基溴化物，搅拌反应；
将反应产物淬灭、洗涤、萃取和干燥，再通过柱层析分离得芳基化吡啶或二嗪化合物。
作为本发明镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法的一种优选方案，其中：所述鏻盐化合物包括(4-三苯基鏻吡啶)三氟甲磺酸盐、(3-甲氧基-4-三苯基鏻吡啶)三氟甲磺酸盐、(3-甲基-4-三苯基鏻基吡啶)三氟甲磺酸盐、(2-苯基-4-三苯基鏻吡啶)三氟甲磺酸盐、(3-苯基-4-三苯基鏻吡啶)三氟甲磺酸盐、(2-(对甲苯基)-4-三苯基鏻吡啶)三氟甲磺酸盐、(5,6,7,8-四氢-4-三苯基鏻喹啉基)三氟甲磺酸盐、(4-甲基-2三苯基鏻喹啉)三氟甲磺酸盐、(4-三苯基鏻喹啉)三氟甲磺酸盐、(2-三苯基鏻吡嗪)三氟甲磺酸盐、(5,6-二甲基-2-三苯基鏻吡嗪)三氟甲磺酸盐、(2-三苯基鏻喹喔啉)三氟甲磺酸盐中的一种。
作为本发明镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法的一种优选方案，其中：所述芳基溴化物包括溴苯、1-溴-4-(三氟甲氧基)苯、1-溴-4-氟苯、4-溴-2-氟-1-甲氧基苯、4-溴-1,1'-联苯、1-溴-4-(叔丁基)苯、1-溴-4-甲基苯、1-溴-3,5-二甲苯、4-溴-1-甲氧基-2-甲基苯、1-溴-4-甲氧基苯、1-溴-3-甲氧基苯、1-溴-2-甲氧基苯、2-溴-1,4-二甲氧基苯、5-溴苯并[1,3]二氧戊环、4-溴-N,N-二苯基苯胺、3-溴-N,N-二甲基苯胺、2-(4-溴苯基)吡啶、2-溴噻吩、4-溴苯并噻吩、2-溴-6-甲氧基萘中的一种。
作为本发明镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法的一种优选方案，其中：所述催化剂包括乙酰丙酮钴、双三苯基膦二氯化钯、氯化铬、氯化亚铁、氯化铜、乙酰丙酮镍、碘化镍、氯化镍二甲醚、氯化镍乙二醇二甲醚、双三苯基膦二氯化镍中的一种。
作为本发明镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法的一种优选方案，其中：所述配体包括1,10-菲咯啉-5,6-二酮、4,7-二苯基-1,10-菲咯啉、2-二环己基膦-2',4',6'-三异丙基联苯、2-二环己膦基-2'-(N,N-二甲胺)-联苯、2-联吡啶、2,9-二甲基-1,10-菲咯啉中的一种。
作为本发明镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法的一种优选方案，其中：所述溶剂包括1，4-二氧六环、二甲醚、2-甲基四氢呋喃、环戊基甲醚、甲基叔丁基醚、四氢吡喃、N,N-二甲基甲酰胺、四氢呋喃。
作为本发明镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法的一种优选方案，其中：所述鏻盐化合物和芳基溴化物的摩尔比为1：3。
作为本发明镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法的一种优选方案，其中：所述搅拌反应，反应温度为0～60℃，反应时间为6～24h。
作为本发明镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法的一种优选方案，其中：所述搅拌反应，反应温度为室温，反应时间为12h。
本发明的另一个目的是提供一种如上述所述的镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法得到的产物，所述产物的化学结构式为：
Figure BDA0003174050630000031
其中，R1包括甲基、甲氧基、三氟甲氧基、吡啶基、苄氧基、二苯氨基、二甲氨基、氟中的一种；
R2包括甲基、甲氧基、苯基、甲基苯基中的一种。
与现有技术相比，本发明具有如下有益效果：
本发明提供了一种从简单易得鏻盐与芳基溴化物原料出发合成吡啶基或二嗪类化合物的新方法，拓展了此类化合物的制备底物范围；该反应使用了便宜易得的芳基卤化物作为偶联底物，使得反应具有了操作便捷性和步骤经济性，因为这避免了使用预制备且对水及空气较为敏感的有机金属化合物；本发明制备方法反应条件温和，具有后处理简单、步骤绿色、污染低、经济效益高等特点。
附图说明
为了更清楚地说明本发明实施例的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其它的附图。其中：
图1为本发明实施例1的目标产物4-苯基吡啶的氢谱；
图2为本发明实施例1的目标产物4-苯基吡啶的碳谱。
图3为本发明实施例2的目标产物N,N-二甲基3-(4-吡啶)苯胺的氢谱；
图4为本发明实施例2的目标产物N,N-二甲基3-(4-吡啶)苯胺的碳谱。
图5为本发明实施例3的目标产物4-甲基-2-苯基喹啉的氢谱；
图6为本发明实施例3的目标产物4-甲基-2-苯基喹啉的碳谱。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合说明书实施例对本发明的具体实施方式做详细的说明。
在下面的描述中阐述了很多具体细节以便于充分理解本发明，但是本发明还可以采用其他不同于在此描述的其它方式来实施，本领域技术人员可以在不违背本发明内涵的情况下做类似推广，因此本发明不受下面公开的具体实施例的限制。
其次，此处所称的“一个实施例”或“实施例”是指可包含于本发明至少一个实现方式中的特定特征、结构或特性。在本说明书中不同地方出现的“在一个实施例中”并非均指同一个实施例，也不是单独的或选择性的与其他实施例互相排斥的实施例。
实施例1
(1)将配有磁力搅拌子的封管放在烘箱中干燥一小时，拿出后趁热塞上橡胶塞并插上一个氮气球；接着称量镁屑(65.4mg,1.5mmol,3equiv.)和氯化锂(84.7mg,2mmol,4equiv.)并加到封管中；随后在减压条件下，使用电加热枪加热镁屑与氯化锂的混合物(320℃，3分钟)；
(2)待混合物降至室温，向其中加入2mL超干四氢呋喃，接着将封管抽换氮气三次。随后向封管中分别加入三苯基(吡啶-4-基)鏻三氟甲磺酸盐(244.7mg,1mmol,1equiv.)、双三苯基膦二氯化钯镍(65.4mg,0.1mmol,20mol％)、1,10-菲咯啉-5,6-二酮(21.0mg,0.1mmol,20mol％)、溴苯(236.4mg,1.5mmol,3equiv.)；混合物在室温下搅拌12小时；
(3)随后使用饱和氯化铵溶液进行淬灭、使用乙酸乙酯进行萃取；萃取液经饱和食盐水洗涤、无水硫酸钠干燥后，通过旋蒸除去萃取液，粗产物通过硅胶柱层析法提纯，柱层析分离条件：固定相为300～400目硅胶粉，流动相为乙酸乙酯(A)和石油醚(B)，流动相变化程序(A:B)为1：5，最终得到57.4mg的目标产物4-苯基吡啶，该化合物结构式为：
Figure BDA0003174050630000051
对上述4-苯基吡啶进行表征，如图1和2所示，结果为：白色固体；1H NMR(400MHz,CDCl3):δ8.66(d,J＝5.6Hz,2H),7.74-7.58(m,2H),7.57-7.41(m,5H)ppm.13C NMR(100MHz,CDCl3):δ150.1,148.4,138.0,129.1,129.1,127.0,121.6ppm.HRMS(ESI,m/z):[M+H]+,calcd.for C11H10N+:156.0808,found:156.0809.FTIR(KBr,neat):ν3058,2923,1588,1483,1410,830,761,730,688,608cm-1.
根据表征数据可知，制得的反应产物为4-苯基吡啶(纯度＞98％)；对产品产率进行计算，结果为74％。
实施例2
(1)将配有磁力搅拌子的封管放在烘箱中干燥一小时，拿出后趁热塞上橡胶塞并插上一个氮气球；接着称量镁屑(65.4mg,1.5mmol,3equiv.)和氯化锂(84.7mg,2mmol,4equiv.)并加到封管中；随后在减压条件下，使用电加热枪加热镁屑与氯化锂的混合物(320℃，3分钟)；
(2)待混合物降至室温，向其中加入2mL超干四氢呋喃，接着将封管抽换氮气三次；随后向封管中分别加入三苯基(吡啶-4-基)鏻三氟甲磺酸盐(244.7mg,1mmol,1equiv.)、双三苯基膦二氯化钯镍(65.4mg,0.1mmol,20mol％)、1,10-菲咯啉-5,6-二酮(21.0mg,0.1mmol,20mol％)、3-溴-N,N-二甲基苯胺(300.4mg,1.5mmol,3equiv.)；混合物在室温下搅拌12小时；
(3)随后使用饱和氯化铵溶液进行淬灭、使用乙酸乙酯进行萃取；萃取液经饱和食盐水洗涤、无水硫酸钠干燥后，通过旋蒸除去萃取液，粗产物通过硅胶柱层析法提纯，柱层析分离条件：固定相为300～400目硅胶粉，流动相为乙酸乙酯(A)和石油醚(B)，流动相变化程序(A:B)为1：5，最终得到57.3mg的目标产物N,N-二甲基-3-(4-吡啶)苯胺，该化合物结构式为：
Figure BDA0003174050630000052
对上述3-N,N-二甲基-4-吡啶基苯胺进行表征，如图3和4所示，结果为：白色固体；1H NMR(400MHz,CDCl3):δ8.65(d,J＝5.2Hz,2H),7.52(d,J＝5.2Hz,2H),7.34(t,J＝7.9Hz,1H),7.00-6.94(m,1H),6.94-6.90(m,1H),6.84-6.79(m,1H),3.01(d,J＝1.2Hz,6H)ppm.13C NMR(100MHz,CDCl3):δ150.9,149.9,149.6,138.9,129.7,121.9,115.1,113.1,110.7,40.5ppm.HRMS(ESI,m/z):[M+H]+,calcd.for C13H15N2 +:199.1230,found:199.1235.FTIR(KBr,neat):ν3024,2892,2809,1594,1546,1400,1235,989,776,698cm-1.
根据表征数据可知，制得的反应产物为3-N,N-二甲基-4-吡啶基苯胺(纯度＞98％)；对产品产率进行计算，结果为58％。
实施例3
(1)将配有磁力搅拌子的封管放在烘箱中干燥一小时，拿出后趁热塞上橡胶塞并插上一个氮气球；接着称量镁屑(65.4mg,1.5mmol,3equiv.)和氯化锂(84.7mg,2mmol,4equiv.)并加到封管中；随后在减压条件下，使用电加热枪加热镁屑与氯化锂的混合物(320℃，3分钟)；
(2)待混合物降至室温，向其中加入2mL超干四氢呋喃，接着将封管抽换氮气三次；随后向封管中分别加入(4-三苯基鏻喹啉)三氟甲磺酸盐(269.6mg,1mmol,1equiv.)、双三苯基膦二氯化钯镍(65.4mg,0.1mmol,20mol％)、1,10-菲咯啉-5,6-二酮(21.0mg,0.1mmol,20mol％)、溴苯(236.4mg,1.5mmol,3equiv.)；混合物在室温下搅拌12小时；
(3)随后使用饱和氯化铵溶液进行淬灭、使用乙酸乙酯进行萃取；萃取液经饱和食盐水洗涤、无水硫酸钠干燥后，通过旋蒸除去萃取液，粗产物通过硅胶柱层析法提纯，柱层析分离条件：固定相为300～400目硅胶粉，流动相为乙酸乙酯(A)和石油醚(B)，流动相变化程序(A:B)为1：5，最终得到58.6mg的目标产物4-苯基喹啉，该化合物结构式为：
Figure BDA0003174050630000061
对上述4-苯基喹啉进行表征，如图5和6所示，结果为：白色固体；1H NMR(400MHz,CDCl3):δ8.94(d,J＝4.4Hz,1H),8.21-8.17(m,1H),7.92(dd,J＝8.5,1.2Hz,1H),7.72(ddd,J＝8.4,6.8,1.4Hz,1H),7.57-7.45(m,6H),7.32(d,J＝4.4Hz,1H)ppm.13C NMR(100MHz,CDCl3):δ149.9,148.6,148.4,137.9,129.8,129.5,129.2,128.5,128.3,126.7,126.5,125.8,121.3ppm.HRMS(ESI,m/z):[M+H]+,calcd.for C15H12N+:206.0964,found:206.0964.FTIR(KBr,neat):ν3058,2923,1583,1574,1507,1490,1444,1390,769,695cm-1.
根据表征数据可知，制得的反应产物为4-苯基喹啉(纯度＞98％)；对产品产率进行计算，结果为57％。
实施例4
实施例4与实施例1基本相同，差别之处在于步骤(2)中溶剂不同，具体如下表1所示：
表1
溶剂 产率(％)
THF 50
DME 38
1,4-dioxane <5
2-MeTHF <5
CpOMe <5
<sup>t</sup>BuOMe <5
THP <5
DMF <5
从表1中可以看出，相同反应条件下，使用不同溶剂，如：1，4-二氧六环、二甲醚、2-甲基四氢呋喃、环戊基甲醚、甲基叔丁基醚、四氢吡喃、N,N-二甲基甲酰胺合成4-苯基吡啶，产率极少量；当以四氢呋喃作溶剂时，反应产率为50％。
实施例5
实施例5与实施例1基本相同，差别之处在于步骤(2)中催化剂不同，具体如下表2所示：
表2
催化剂 产率(％)
Co(acac)<sub>2</sub> 21
Pd(PPh<sub>3</sub>)<sub>2</sub>Cl<sub>2</sub> 16
CrCl<sub>2</sub> 7
FeCl<sub>2</sub> 16
CuCl<sub>2</sub> 8
Ni(acac)<sub>2</sub> 44
NiI<sub>2</sub> 19
NiCl<sub>2</sub>·DME 42
NiCl<sub>2</sub>·glyme 47
Ni(PPh<sub>3</sub>)<sub>2</sub>Cl<sub>2</sub> 50
从表2中可以看出，相同反应条件下，使用不同催化剂，如：乙酰丙酮钴、双三苯基膦二氯化钯、氯化铬、氯化亚铁、氯化铜、乙酰丙酮镍、碘化镍、氯化镍二甲醚、氯化镍乙二醇二甲醚合成4-苯基吡啶，产率较低；当以双三苯基膦二氯化镍作催化剂时，反应产率为50％。
实施例6
实施例6与实施例1基本相同，差别之处在于步骤(2)中催化剂当量和温度不同，具体如下表3所示：
表3
Figure BDA0003174050630000081
Figure BDA0003174050630000091
从表3中可以看出，在0～60℃范围内的不同温度下均能得到目标产物，其中，室温最优，产率最高；
在室温条件下，双三苯基膦二氯化镍的用量为20mol％，合成4-苯基吡啶最高，产率为63％。
实施例7
实施例7与实施例1基本相同，差别之处在于步骤(2)中配体不同，具体如下表4所示：
表4
Figure BDA0003174050630000092
Figure BDA0003174050630000101
从表4中可以看出，相同反应条件下，对不同的配体，如：1,10-菲咯啉-5,6-二酮、4,7-二苯基-1,10-菲咯啉、2-二环己基膦-2',4',6'-三异丙基联苯、2-二环己膦基-2'-(N,N-二甲胺)-联苯、2-联吡啶、2,9-二甲基-1,10-菲咯啉等配体合成4-苯基吡啶，以1,10-菲咯啉-5,6-二酮效果最优，产率最高为77％。
实施例8
实施例8与实施例1基本相同，差别之处在于步骤(2)中，芳基鏻盐和芳基溴化物不同，具体如下表5所示：
表5
Figure BDA0003174050630000102
Figure BDA0003174050630000111
Figure BDA0003174050630000121
本发明提供了一种从简单易得鏻盐与芳基溴化物原料出发合成吡啶基或二嗪类化合物的新方法，拓展了此类化合物的制备底物范围；该反应使用了便宜易得的芳基卤化物作为偶联底物，使得反应具有了操作便捷性和步骤经济性，因为这避免了使用预制备且对水及空气较为敏感的有机金属化合物；本发明制备方法反应条件温和，具有后处理简单、步骤绿色、污染低、经济效益高等特点。
应说明的是，以上实施例仅用以说明本发明的技术方案而非限制，尽管参照较佳实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围，其均应涵盖在本发明的权利要求范围当中。

Claims (10)

1.一种镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法，其特征在于：包括，
在氮气氛围下，加热镁屑与氯化锂的混合物；
待混合物降至室温，向其中加入超干溶剂；随后分别加入鏻盐化合物、催化剂、配体和芳基溴化物，搅拌反应；
将反应产物淬灭、洗涤、萃取和干燥，再通过柱层析分离得芳基化吡啶或二嗪化合物。
2.如权利要求1所述的镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法，其特征在于：所述鏻盐化合物包括(4-三苯基鏻吡啶)三氟甲磺酸盐、(3-甲氧基-4-三苯基鏻吡啶)三氟甲磺酸盐、(3-甲基-4-三苯基鏻基吡啶)三氟甲磺酸盐、(2-苯基-4-三苯基鏻吡啶)三氟甲磺酸盐、(3-苯基-4-三苯基鏻吡啶)三氟甲磺酸盐、(2-(对甲苯基)-4-三苯基鏻吡啶)三氟甲磺酸盐、(5,6,7,8-四氢-4-三苯基鏻喹啉基)三氟甲磺酸盐、(4-甲基-2三苯基鏻喹啉)三氟甲磺酸盐、(4-三苯基鏻喹啉)三氟甲磺酸盐、(2-三苯基鏻吡嗪)三氟甲磺酸盐、(5,6-二甲基-2-三苯基鏻吡嗪)三氟甲磺酸盐、(2-三苯基鏻喹喔啉)三氟甲磺酸盐中的一种。
3.如权利要求1或2所述的镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法，其特征在于：所述芳基溴化物包括溴苯、1-溴-4-(三氟甲氧基)苯、1-溴-4-氟苯、4-溴-2-氟-1-甲氧基苯、4-溴-1,1'-联苯、1-溴-4-(叔丁基)苯、1-溴-4-甲基苯、1-溴-3,5-二甲苯、4-溴-1-甲氧基-2-甲基苯、1-溴-4-甲氧基苯、1-溴-3-甲氧基苯、1-溴-2-甲氧基苯、2-溴-1,4-二甲氧基苯、5-溴苯并[1,3]二氧戊环、4-溴-N,N-二苯基苯胺、3-溴-N,N-二甲基苯胺、2-(4-溴苯基)吡啶、2-溴噻吩、4-溴苯并噻吩、2-溴-6-甲氧基萘中的一种。
4.如权利要求3所述的镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法，其特征在于：所述催化剂包括乙酰丙酮钴、双三苯基膦二氯化钯、氯化铬、氯化亚铁、氯化铜、乙酰丙酮镍、碘化镍、氯化镍二甲醚、氯化镍乙二醇二甲醚、双三苯基膦二氯化镍中的一种。
5.如权利要求1、2或4任一所述的镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法，其特征在于：所述配体包括1,10-菲咯啉-5,6-二酮、4,7-二苯基-1,10-菲咯啉、2-二环己基膦-2',4',6'-三异丙基联苯、2-二环己膦基-2'-(N,N-二甲胺)-联苯、2-联吡啶、2,9-二甲基-1,10-菲咯啉中的一种。
6.如权利要求5所述的镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法，其特征在于：所述溶剂包括1，4-二氧六环、二甲醚、2-甲基四氢呋喃、环戊基甲醚、甲基叔丁基醚、四氢吡喃、N,N-二甲基甲酰胺、四氢呋喃。
7.如权利要求1、2、4或6任一所述的镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法，其特征在于：所述鏻盐化合物和芳基溴化物的摩尔比为1：3。
8.如权利要求7所述的镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法，其特征在于：所述搅拌反应，反应温度为0～60℃，反应时间为6～24h。
9.如权利要求8所述的镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法，其特征在于：所述搅拌反应，反应温度为室温，反应时间为12h。
10.一种如权利要求1～9中任一所述的镍催化的杂环鏻盐与芳基溴的直接还原交叉偶联方法得到的产物，其特征在于：所述产物的化学结构式为：
Figure FDA0003174050620000021
其中，R1包括甲基、甲氧基、三氟甲氧基、吡啶基、苄氧基、二苯氨基、二甲氨基、氟中的一种；
R2包括甲基、甲氧基、苯基、甲基苯基中的一种。
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CN114591128A (zh) * 2022-02-25 2022-06-07 南京工业大学 一种芳基硫盐与芳基溴的直接交叉偶联方法
CN114591128B (zh) * 2022-02-25 2023-08-22 南京工业大学 一种芳基硫盐与芳基溴的直接交叉偶联方法
CN114702437A (zh) * 2022-04-15 2022-07-05 南京工业大学 一种杂芳基鏻盐与末端炔烃的Sonogashira偶联方法
CN116283515A (zh) * 2023-03-17 2023-06-23 南京工业大学 一种芳基氟与芳基溴的直接交叉偶联方法
CN116283515B (zh) * 2023-03-17 2024-05-28 南京工业大学 一种芳基氟与芳基溴的直接交叉偶联方法

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