CN114957312A - 一种共轭烯烃的芳硅化合物及其制备方法与应用 - Google Patents
一种共轭烯烃的芳硅化合物及其制备方法与应用 Download PDFInfo
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- CN114957312A CN114957312A CN202210452855.2A CN202210452855A CN114957312A CN 114957312 A CN114957312 A CN 114957312A CN 202210452855 A CN202210452855 A CN 202210452855A CN 114957312 A CN114957312 A CN 114957312A
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- compound
- conjugated olefin
- quinolin
- arylsilicon
- oxo
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Classifications
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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Abstract
本发明公开了一种共轭烯烃的芳硅化合物及其制备方法与应用。在惰性气氛下,本发明通过将摩尔体积比为0.1mmol:1~3mL的材料、溶剂混匀在反应容器中,将反应容器置于80~120℃油浴中剧烈搅拌反应12~36小时,得到反应产物;其中,所述材料包括按摩尔比为1:1~3:2~5:0.01~0.15:0.02~0.2:10~30的共轭烯烃化合物、芳基溴化物、(二甲基苯甲硅烷基)硼酸频哪醇脂、钯催化剂、配位化合物及硅硼键活化物,再将反应产物经过硅胶柱纯化,得到共轭烯烃的芳硅化合物,该共轭烯烃的芳硅化合物可应用在芳硅化合物的官能团转化中。本发明芳硅化合物制备方法具有产率高、反应条件温和、反应及后处理纯化过程简单,易于操作等特点,所得芳硅化合物具有良好的区域选择性。
Description
技术领域
本发明属于有机化合物的合成技术领域,尤其涉及一种共轭烯烃的芳硅化合物及其制备方法与应用。
背景技术
含硅化合物在有机合成、药物化学和材料科学中有着非常广泛的应用,由于含硅化合物具有以下特点:(1)形成的C-Si键比C-C键键长更长,可以改变分子与受体的结合方式;(2)含硅的分子具有更高的亲脂性,可以改善药物的穿透性。因此,各种类型的硅试剂已被开发并应用于有机合成中,如Hoveyda课题组最早利用α,β-不饱和烯烃结构,在路易斯碱条件下活化硅硼(Si-B)键,烯烃的芳硅化将两个基团引入到一个分子中,这项工作提供了一种合成具有高度官能化的硅烷化的新策略。
迄今为止,成功合成烯烃的芳硅化合物的有机方法概况为:
(1)文献(Li,J.Angew.Chem.2022,1433-7851.)记载的方法:
(2)文献(Nozaki,K.J.Org.Chem.2016,81,3065-3069.)记载的方法:
综上所述,目前合成烯烃的芳硅化合物的方法很少,而使用α,β-不饱和烯烃合成共轭烯烃的芳硅化合物的更是寥寥无几,因此合成共轭烯烃的芳硅化合物具有重要意义。
发明内容
为克服现有技术的缺点和不足,本发明的首要目的在于提供上述共轭烯烃的芳硅化合物的制备方法。
本发明的再一目的在于提供一种由上述制备方法得到的共轭烯烃的芳硅化合物。
本发明的另一目的在于提供上述共轭烯烃的芳硅化合物的应用。
本发明是这样实现的,一种共轭烯烃的芳硅化合物,该化合物的分子结构式如下式(I)所示:
R1选自氢基、甲基、苯基、苄基中的任意一种;
R2选自氢基、苯基中的任意一种;
Ar选自苯基、叔丁基苯基、三氟甲氧基苯基、氟苯基、苯乙酮基、三氟甲苯基、间位氟苯基、间苯甲醚基、间苯甲酸甲酯基、邻苯甲酸甲酯基、2-甲基苯甲醚基、1-氟-3-三氟甲苯基、3-(三氟甲基)苯甲醚基、2,6-二甲基氟苯基、苯并呋喃基、苯并噁唑基、噻吩基、芴基、N-苯基咔唑基、4-甲氧基苯乙烯基中的任意一种;
EWG选自氰基、甲脂基、乙酯基、叔丁酯基、正丁酯基、苯甲酮基、乙基酮基、丙基酮基中的任意一种。
本发明进一步公开了一种共轭烯烃的芳硅化合物的制备方法,该制备方法包括以下步骤:
(1)在惰性气氛下,将摩尔体积比为0.1mmol:1~3mL的材料、溶剂混匀在反应容器中,将反应容器置于80~120℃油浴中剧烈搅拌反应12~36小时,得到反应产物;其中,所述材料包括按摩尔比为1:1~3:2~5:0.01~0.15:0.02~0.2:10~30的共轭烯烃化合物、芳基溴化物、(二甲基苯甲硅烷基)硼酸频哪醇脂、钯催化剂、配位化合物及硅硼键活化物;
(2)将反应产物经过硅胶柱纯化,得到共轭烯烃的芳硅化合物。
优选地,在步骤(1)中,所述芳基溴化物选自溴苯、对叔丁基溴苯、对溴三氟甲氧基苯、对溴氟苯、对溴苯乙酮、对溴三氟甲苯、3-氟溴苯、3-溴苯甲醚、3-溴苯甲酸甲酯、邻溴苯甲酸甲酯、2-甲基-4-溴苯甲醚、3-溴-5-氟三氟甲苯、3-溴-5-三氟甲基苯甲醚、4-溴-2,6-二甲基氟苯、5-溴苯并呋喃、6-溴苯并恶唑、2-溴噻吩、2-溴芴、2-溴-N-苯基咔唑、1-(2-溴乙烯基)-4-甲氧基苯中的任意一种。
优选地,在步骤(1)中,所述共轭烯烃化合物选自甲基(E)-6-氧代-6-(喹啉-8-氨基)己基-2-烯酸酯、乙基(E)-6-氧代-6-(喹啉-8-氨基)己基-2-烯酸酯、叔丁基(E)-6-氧代-6-(喹啉-8-氨基)己基-2-烯酸酯、正丁基(E)-6-氧代-6-(喹啉-8-氨基)己基-2-烯酸酯、甲基(E)-5-甲基-6-氧代-6-(喹啉-8-氨基)己基-2-烯酸酯、甲基(E)-5-苯基-6-氧代-6-(喹啉-8-氨基)己基-2-烯酸酯、甲基(E)-5-苄基-6-氧代-6-(喹啉-8-氨基)己基-2-烯酸酯、(E)-6-氧代-6-(喹啉-8-基)庚基-4-烯酰胺、(E)-6-氧代-6-(喹啉-8-基)辛基-4-烯酰胺、(E)-6-氧代-6-苯基--6-(喹啉-8-基)庚基-4-烯酰胺以及(E)-氰基-N-(喹啉-8-基)戊基-4-烯酰胺中的任意一种。
优选地,在步骤(1)中,所述钯催化剂选自双乙腈氯化钯、1,5-环辛二烯二氯化钯、三(二亚苄基丙酮)二钯、二氯化钯以及醋酸钯中的任意一种。
优选地,在步骤(1)中,所述配位化合物选自2-(二叔丁基膦)-1-(2-甲氧苯基)-1H-吡咯、2-二叔丁基磷-2-(N,N-二甲氨基)联苯、2-二叔丁基膦-1-苯基吲哚、2-二环己基膦-2'6'-双(N,N-二甲胺基)-1,1'-联苯、1-[2-(二叔丁基膦)苯基]-3,5-二苯基-1H-吡唑中的任意一种。
优选地,在步骤(1)中,所述硅硼键活化物选自N,N-二异丙基乙胺、N,N-二己基甲胺以及氟化钾中的任意一种。
优选地,在步骤(1)中,在步骤(1)中,所述溶剂选自乙腈、四氢呋喃、N,N-二甲基甲酰胺、1,2-二氯乙烷、甲苯中的任意一种。
优选地,在步骤(1)中,所述共轭烯烃化合物、芳基溴化物、(二甲基苯甲硅烷基)硼酸频哪醇脂、钯催化剂、配位化合物及硅硼键活化物的摩尔比为1:1.5:3:0.05:0.1:10;
在步骤(1)中,所述将反应容器置于100℃油浴中剧烈搅拌反应36小时;
在步骤(1)中,所述惰性气氛为氩气氛围;
在步骤(2)中,所述硅胶柱纯化的洗脱剂为PE:EA=15:1~5:1。
本发明进一步公开了上述共轭烯烃的芳硅化合物的官能团转化在芳硅化合物中的应用。
本发明克服现有技术的不足,提供一种共轭烯烃的芳硅化合物及其制备方法与应用。在惰性气氛下,本发明通过将共轭烯烃化合物、芳基溴化物、(二甲基苯甲硅烷基)硼酸频哪醇脂、钯催化剂、配位化合物、硅硼键活化物以及溶剂混匀在反应容器中,将反应容器置于80~120℃油浴中剧烈搅拌反应12~36小时,得到反应产物,其中,配位化合物参与反应中的配位作用并稳定六元钯环中间体,硅硼键活化物则用于活化硅硼键,使其发生转金属化。
在本发明芳硅化合物的制备方法中,芳基溴代物在Pd作用下发生氧化加成,形成的RPd(II)X中间体进一步与具有导向基团的烯烃底物发生配位并进行1,2-移位插入,形成六元烷基钯环中间体,随后亲核试剂(PhMe2Si-Bpin)通过转金属化来截取螯合稳定的六元烷基钯环中间体,经过还原消除最终合成芳硅化产物。与现有技术相比,本发明设计八氨基喹啉作为导向基团的共轭烯烃来控制反应中的区域选择性和化学选择性,能有效克服电子效应,具有杰出的区域选择性和底物的普适性。
本发明芳硅化合物的合成过程如下所示:
相比于现有技术的缺点和不足,本发明具有以下有益效果:本发明芳硅化合物制备方法具有产率高、反应条件温和、反应及后处理纯化过程简单,易于操作等特点,所得芳硅化合物具有良好的区域选择性,该方法为现代有机合成工作者提供了一个新的反应设计思路。
附图说明
图1是本发明共轭烯烃的芳硅化合物1的1H NMR核磁谱图;
图2是本发明共轭烯烃的芳硅化合物1的13C NMR核磁谱图;
图3是本发明共轭烯烃的芳硅化合物2的1H NMR核磁谱图;
图4是本发明共轭烯烃的芳硅化合物2的13C NMR核磁谱图;
图5是本发明共轭烯烃的芳硅化合物2的F NMR核磁谱图;
图6是本发明共轭烯烃的芳硅化合物3的1H NMR核磁谱图;
图7是本发明共轭烯烃的芳硅化合物3的13C NMR核磁谱图;
图8是本发明共轭烯烃的芳硅化合物4的1H NMR核磁谱图;
图9是本发明共轭烯烃的芳硅化合物4的13C NMR核磁谱图;
图10是本发明共轭烯烃的芳硅化合物5的1H NMR核磁谱图;
图11是本发明共轭烯烃的芳硅化合物5的13C NMR核磁谱图;
图12是本发明共轭烯烃的芳硅化合物6的1H NMR核磁谱图;
图13是本发明共轭烯烃的芳硅化合物6的13C NMR核磁谱图。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合附图及实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。
本发明实施例中所使用的所有化学试剂中,共轭烯烃化合物2a~2i均根据文献(ACS Catal.2020,10,7262-7268.)记载的方法合成得到,其他原料均购自市场。本发明实施例中所使用的仪器:400M Jeol核磁共振仪、气相色谱仪使用的型号是岛津GC2010plus、气质色谱联用仪使用的型号是赛默飞ISQ单重四极杆、液质色谱联用仪的型号是赛默飞UltiMate 3000单重四极杆。
为简洁、方便表达,在下述实施例中所选用的芳基溴化物做如下编号(芳基溴化物1a~1t):
其中,1a:溴苯,1b:对叔丁基溴苯,1c:对溴三氟甲氧基苯,1d:对溴氟苯,1e:对溴苯乙酮,1f:对溴三氟甲苯,1g:3-氟溴苯,1h:3-溴苯甲醚,1i:3-溴苯甲酸甲酯,1j:邻溴苯甲酸甲酯,1k:2-甲基-4-溴苯甲醚,1l:3-溴-5-氟三氟甲苯,1m:3-溴-5-三氟甲基苯甲醚,1n:4-溴-2,6-二甲基氟苯,1o:5-溴苯并呋喃,1p:6-溴苯并恶唑,1q:2-溴噻吩,1r:2-溴芴,1s:2-溴-N-苯基咔唑,1t:1-(2-溴乙烯基)-4-甲氧基苯。
在下述实施例中所选用的共轭烯烃化合物做如下编号(共轭烯烃化合物2a~2i):
其中,2a:甲基(E)-6-氧代-6-(喹啉-8-氨基)己基-2-烯酸酯,
2b:乙基(E)-6-氧代-6-(喹啉-8-氨基)己基-2-烯酸酯,
2c:叔丁基(E)-6-氧代-6-(喹啉-8-氨基)己基-2-烯酸酯,
2d:正丁基(E)-6-氧代-6-(喹啉-8-氨基)己基-2-烯酸酯,
2e:甲基(E)-5-甲基-6-氧代-6-(喹啉-8-氨基)己基-2-烯酸酯,
2f:甲基(E)-5-苯基-6-氧代-6-(喹啉-8-氨基)己基-2-烯酸酯,
2g:甲基(E)-5-苄基-6-氧代-6-(喹啉-8-氨基)己基-2-烯酸酯,
2h:(E)-6-氧代-6-(喹啉-8-基)庚基-4-烯酰胺,
2i:(E)-6-氧代-6-(喹啉-8-基)辛基-4-烯酰胺,
2j:(E)-6-氧代-6-苯基--6-(喹啉-8-基)庚基-4-烯酰胺,
2k:(E)-氰基-N-(喹啉-8-基)戊基-4-烯酰胺。
实施例1
(1)在氩气环境下,向含有磁力搅拌子的25mL Schlenk管中有序地加入0.2mmol(约58mg)共轭烯烃化合物2a,0.3mmol(约32uL)芳基溴化物1a,0.6mmol(约164uL)(二甲基苯甲硅烷基)硼酸频哪醇脂,0.01mmol(5.2mg)双乙腈二氯化钯,0.02mmol(约12.8mg)2-(二叔丁基膦)-1-(2-甲氧苯基)-1H-吡咯,0.6mmol(约52uL)N,N-二异丙基乙胺,加到2mL乙腈中,将管紧紧盖住,并将混合物在预热的100℃油浴中剧烈搅拌24小时即可反应结束;
(2)将反应产物过硅胶柱纯化(洗脱剂为PE:EA=15:1~5:1),得到72mg共轭烯烃的芳硅化合物1,产率为72%。
对芳硅化合物1进行表征,结果如图1~2所示,图1是其1H NMR核磁谱图、图2是其13C NMR核磁谱图。
芳硅化合物1的表征数据为:
1H NMR(400MHz,CDCl3):δ9.69(s,1H),8.79(dd,J=4.2,1.7Hz,1H),8.76(dd,J=3.7,1.7Hz,1H),8.17(dd,J=8.2,1.6Hz,1H),7.56-7.42(m,5H),7.33-7.27(m,3H),7.23-7.13(m,5H),3.73-3.69(m,1H),3.48(s,3H),2.64-2.59(m,1H),2.52-2.46(m,1H),2.15-2.08(m,2H),1.47-1.40(m,1H),0.29(s,6H).
13C NMR(100MHz,CDCl3):δ174.76,171.68,148.17,138.56,137.40,134.13,129.20,128.65,128.48,127.97,127.60,127.27,121.69,121.48,52.01,50.26,39.05,34.11,19.64,-4.11,-4.56.
该芳硅化合物1的化学结构式为:
实施例2
(1)在氩气环境下,向含有磁力搅拌子的干燥的25mL Schlenk管中有序地加入0.2mmol共轭烯烃化合物2a,0.2mmol芳基溴化物1I(3-溴-5-氟三氟甲苯),0.4mmol(二甲基苯甲硅烷基)硼酸频哪醇脂,0.002mmol双乙腈二氯化钯,0.004mmol 2-(二叔丁基膦)-1-(2-甲氧苯基)-1H-吡咯,0.2mmol N,N-二异丙基乙胺,加到2m乙腈中,将管紧紧盖住,并将混合物在预热的100℃油浴中剧烈搅拌36小时即可反应结束;
(2)将反应产物过硅胶柱纯化(洗脱剂为PE:EA=15:1~5:1),得到104mg共轭烯烃的芳硅化合物2,产率为61%。
将芳硅化合物2进行表征,结果如图3~5所示,其中,图3是其1H NMR核磁谱图,图4是其13C NMR核磁谱图,图5是其F NMR核磁谱图。
芳硅化合物2的表征数据为:
1H NMR(400MHz,CDCl3):δ9.72(m,1H),8.83-8.72(m,2H),8.18(dd,J=8.3,1.7Hz),7.58-7.43(m,5H),7.39-7.30(m,3H),7.17-7.00(m,3H),3.77-3.72(m,1H),3.57-3.50(m,3H),2.70(dd,J=15.1,4.6Hz,1H),2.48-2.36(m,1H),2.11-2.07(m,1H),1.82-1.75(m,0.5H),1.62-1.59(m,0.5H),1.43-1.38(m,1H),0.41(d,J=17.1Hz),0.32(s,3H).
13C NMR(100MHz,CDCl3):δ173.55,173.08,171.53,171.47,148.26,142.89,142.81,142.28,142.21,138.41,138.37,137.34,136.88,136.54,136.53,134.46,134.43,134.12,133.96,129.54,128.18,128.15,128.09,128.08,127.60,127.57,121.76,121.74,121.70,121.68,116.63,116.60,53.56,52.33,50.17,50.15,50.05,50.02,39.10,38.97,34.87,34.40,31.64,30.27,29.84,20.89,19.67,-4.16,-4.19,-4.45,-5.01.
该芳硅化合物2的化学结构式为:
实施例3
(1)在氩气环境下,向含有磁力搅拌子的25mL Schlenk管中有序地加入0.2mmol共轭烯烃化合物2a,1mmol(二甲基苯甲硅烷基)硼酸频哪醇脂,0.6mmol芳基溴化物1q(2-溴噻吩),0.03mmol双乙腈二氯化钯,0.04mmol 2-(二叔丁基膦)-1-(2-甲氧苯基)-1H-吡咯,5mmol N,N-二异丙基乙胺,加到6mL乙腈中,将管紧紧盖住,并将混合物在预热的100℃油浴中剧烈搅拌36小时即可反应结束;
(2)将反应产物过硅胶柱纯化(洗脱剂为PE:EA=15:1~5:1),得到70mg共轭烯烃的芳硅化合物3,产率为65%。
对芳硅化合物3进行表征,结果如图6~7所示,其中,图6是其1H NMR核磁谱图,图7是其13C NMR核磁谱图。
芳硅化合物3的表征数据为:
1H NMR(400MHz,CDCl3):δ9.68(m,1H),8.80-8.72(m,2H),8.18-8.15(m,1H),7.57–7.45(m,5H),7.34-7.26(m,3H),7.17-7.15(m,0.5H),7.08-7.06(m,0.5H),6.87-6.78(m,2H),4.13-4.03(m,1H),3.60-3.49(m,3H),2.66-2.58(m,1H),2.50-2.41(m,1H),2.21-2.06(m,1H),1.89-1.82(m,0.5H),1.68-1.63(m,0.5H),1.57-1.53(m,1H),0.40(d,J=4.8Hz,3H),0.32(d,J=2.7Hz,3H).
13C NMR(100MHz,CDCl3):δ173.94,173.34,171.54,171.49,141.83,140.81,137.41,137.22,136.48,134.18,134.15,129.32,129.26,128.04,128.00,127.59,126.69,126.64,126.45,125.37,124.90,124.46,121.51,121.47,116.61,52.28(d,J=2.4Hz),45.82,45.73,38.81,36.05,35.67,20.91,19.69,-4.05,-4.25,-4.28,-4.35.
芳硅化合物3的化学结构式为:
实施例4
(1)在氩气环境下,向含有磁力搅拌子的25mL Schlenk管中有序地加入0.2mmol共轭烯烃化合物2c,0.6mmol(二甲基苯甲硅烷基)硼酸频哪醇脂,0.3mmol芳基溴化物1k(4-溴-2-甲基苯甲醚),0.01mmol双乙腈二氯化钯,0.02mmol 2-(二叔丁基膦)-1-(2-甲氧苯基)-1H-吡咯,3mmol N,N-二异丙基乙胺,加到2mL乙腈中,将管紧紧盖住,并将混合物在预热的100℃油浴中剧烈搅拌36小时即可反应结束;
(8)将反应产物过硅胶柱纯化(洗脱剂为PE:EA=15:1~5:1),得到90mg共轭烯烃的芳硅化合物6,产率为76%。
对芳硅化合物4进行表征,结果如图8~9所示,其中,图8是其1H NMR核磁谱图,图9是其13C NMR核磁谱图。
芳硅化合物4的表征数据为:
1H NMR(400MHz,CDCl3):δ9.70-9.68(m,1H),8.79-8.73(m,2H),8.16(dd,J=8.3,1.7Hz,1H),7.62-7.38(m,6H),7.31-7.26(m,2H),7.21-7.17(m,2H),7.14-7.04(m,2H),3.68-3.52(m,1H),2.63-2.38(m,2H),2.09-1.97(m,1H),1.49-1.43(m,1H),1.29-1.23(m,18H),0.42-0.42(m,1H),0.39-0.37(m,2H),0.31-0.30(m,4H).
13C NMR(100MHz,CDCl3):δ173.75,173.08,171.77,171.64,171.36,149.49,148.63,147.23,138.38,137.63,136.95,136.43,135.88,134.61,134.20,134.12,133.16,129.74,129.12,129.08,128.01,127.99,127.92,127.89,127.85,127.56,127.54,127.41,125.37,125.29,121.66,121.38,116.52,80.40,60.56,50.72,39.44,34.43,31.44,31.39,28.03,27.93,21.22,19.69,14.32,0.14,-3.92,-4.29,-4.42.
芳硅化合物4的化学结构式为:
实施例5
(1)在氩气环境下,向含有磁力搅拌子的25mL Schlenk管中有序地加入0.2mmol共轭烯烃化合物2e,0.6mmol(二甲基苯甲硅烷基)硼酸频哪醇脂,0.3mmol芳基溴化物1k(4-溴-2-甲基苯甲醚),0.01mmol 1,5-环辛二烯二氯化钯5.7mg,2-二叔丁基膦-1-苯基吲哚,0.02mmol N,N-二异丙基乙胺,加到2mL乙腈中,将管紧紧盖住,并将混合物在预热的100℃油浴中剧烈搅拌36小时即可反应结束;
(8)将反应产物过硅胶柱纯化(洗脱剂为PE:EA=15:1~5:1),得到72mg共轭烯烃的芳硅化合物5,产率为65%。
对芳硅化合物5进行表征,结果如图10~11所示,其中,图10是其1H NMR核磁谱图,图11是其13C NMR核磁谱图。
芳硅化合物5的表征数据为:
1H NMR(400MHz,CDCl3):δ9.84-9.71(m,1H),8.82-8.68(m,2H),8.17-8.14(m,1H),7.59-7.30(m,7H),7.25-7.21(m,1H),6.97-6.65(m,2.5H),6.32(d,J=8.3Hz,0.5H),3.79-3.49(m,7H),2.84-2.74(m,1H),2.43-2.23(m,1H),2.08-1.95(m,2H),1.26-1.24(m,3H),0.48-0.23(m,6H).
13C NMR(100MHz,CDCl3):δ175.59,175.22,174.67,174.41,156.93,156.64,148.15,148.12,138.95,138.61,138.55,138.17,136.40,136.32,134.81,134.56,134.10,134.04,130.64,130.49,130.43,129.50,129.15,128.93,128.03,127.99,127.86,127.63,127.56,126.86,126.68,126.32,126.14,121.65,121.37,121.25,116.54,116.38,109.84,109.48,55.34,55.13,52.09,51.94,49.82,48.88,43.09,41.04,32.92,29.84,29.65,28.25,26.48,16.41,16.33,16.03,14.45,-2.63,-2.83,-2.95,-3.72.
芳硅化合物5的化学结构式为:
实施例6
(1)在氩气环境下,向含有磁力搅拌子的25mL Schlenk管中有序地加入0.2mmol共轭烯烃化合物2a,0.6mmol(二甲基苯甲硅烷基)硼酸频哪醇脂,0.3mmol芳基溴化物1k(4-溴-2-甲基苯甲醚),0.01mmol 1,5-环辛二烯二氯化钯,0.02mmol 2-二叔丁基膦-1-苯基吲哚,0.06mmol N,N-二异丙基乙胺,加到2mL乙腈中,将管紧紧盖住,并将混合物在预热的100℃油浴中剧烈搅拌36小时即可反应结束;
(8)将反应产物过硅胶柱纯化(洗脱剂为PE:EA=15:1~5:1),得到60mg共轭烯烃的芳硅化合物6,产率为57%。
对芳硅化合物6进行表征,结果如图12~13所示,其中,图12是其1H NMR核磁谱图,图13是其13C NMR核磁谱图。
芳硅化合物6的表征数据为:
1H NMR(400MHz,CDCl3):δ9.82-9.67(m,1H),8.79-8.75(m,2H),8.18-8.16(m,1H),7.59-7.44(m,6H),7.06-6.93(m,4H),6.82-6.78(m,3H),6.73-6.68(m,3H),6.58-6.56(m,0.3H),6.03-5.99(m,0.7H),3.84-3.81(m,6H),3.68(s,1H),2.68-2.66(m,4H),2.38-2.28(m,2H),2.17-2.15(m,6H),1.95(d,J=25.2Hz,3H).
13C NMR(100MHz,CDCl3):δ208.68,172.30,171.31,157.11,156.86,156.82,142.70,137.81,136.50,135.37,134.62,134.23,132.16,132.06,130.86,130.51,129.72,129.27,128.33,128.05,127.59,127.00,126.41,126.29,126.10,125.32,121.75,121.69,121.51,110.02,109.56,109.43,57.45,55.47,55.38,55.26,39.61,38.67,29.48,26.16,16.42,14.35,14.28,0.15,-4.18,-4.52.
芳硅化合物6的化学结构式为:
实施例7~10
实施例7~10与实施例1基本相同,不同之处如下表1所示:
表1
应用实施例
在本发明实施例中,共轭烯烃的芳硅化合物可以进行官能团转化。根据现有文献的记载,其应用方式包括:
(1)文献1(ACS Catal.2021,11,1858-1862.)记载的方法:
(2)文献2(J.Am.Chem.Soc.2010,132,2898.)记载的方法:
基于相同的原理和过程,本发明共轭烯烃的芳硅化合物可以进行如下应用:
该反应包括以下具体步骤:
(1)在氩气条件下,向含有搅拌子的25mL Schlenk管中有序地加入100mg芳硅化合物1、136.1mg双(2,2,6,6,-四甲基-3,5-庚二酮)镍,然后再加入2mL甲醇,该反应在100℃油浴锅中反应四天;
(2)反应结束之后,将反应产物冷却至室温,用乙酸乙酯萃取反应液,合并有机相,用无水硫酸钠干燥,旋干,将该反应瓶在氮气环境下抽换三次,加入2mL超干的二氯甲烷,然后把反应瓶放入0℃冰水浴中,再逐滴加入HBF4·Et2O(54μL,0.20mmol),取样监测反应;
(3)反应完全后用硫代硫酸钠淬灭反应,用乙醚萃取反应液,合并有机相,用无水硫酸钠干燥,旋干,在反应瓶中加入甲醇和四氢呋喃各1mL,再加入35mg氟化钾和50mg碳酸氢钠,放在0℃冰水浴中搅拌,再逐滴加入30%过氧化氢,然后再室温下反应,取样监测反应;
(4)反应完全后用硫代硫酸钠淬灭反应,乙醚萃取反应液,合并有机相,用无水硫酸钠干燥,浓缩,使用石油醚和乙酸乙酯作为洗脱剂通过硅胶柱纯化,得到目标化合物。
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。
Claims (10)
2.一种共轭烯烃的芳硅化合物的制备方法,其特征在于,该制备方法包括以下步骤:
(1)在惰性气氛下,将摩尔体积比为0.1mmol:1~3mL的材料、溶剂混匀在反应容器中,将反应容器置于80~120℃油浴中剧烈搅拌反应12~36小时,得到反应产物;其中,所述材料包括按摩尔比为1:1~3:2~5:0.01~0.15:0.02~0.2:10~30的共轭烯烃化合物、芳基溴化物、(二甲基苯甲硅烷基)硼酸频哪醇脂、钯催化剂、配位化合物及硅硼键活化物;
(2)将反应产物经过硅胶柱纯化,得到共轭烯烃的芳硅化合物。
3.如权利要求2所述的共轭烯烃的芳硅化合物的制备方法,其特征在于,在步骤(1)中,所述芳基溴化物选自溴苯、对叔丁基溴苯、对溴三氟甲氧基苯、对溴氟苯、对溴苯乙酮、对溴三氟甲苯、3-氟溴苯、3-溴苯甲醚、3-溴苯甲酸甲酯、邻溴苯甲酸甲酯、2-甲基-4-溴苯甲醚、3-溴-5-氟三氟甲苯、3-溴-5-三氟甲基苯甲醚、4-溴-2,6-二甲基氟苯、5-溴苯并呋喃、6-溴苯并噁唑、2-溴噻吩、2-溴芴、2-溴-N-苯基咔唑、1-(2-溴乙烯基)-4-甲氧基苯中的任意一种。
4.如权利要求2所述的共轭烯烃的芳硅化合物的制备方法,其特征在于,在步骤(1)中,所述共轭烯烃化合物选自甲基(E)-6-氧代-6-(喹啉-8-氨基)己基-2-烯酸酯、乙基(E)-6-氧代-6-(喹啉-8-氨基)己基-2-烯酸酯、叔丁基(E)-6-氧代-6-(喹啉-8-氨基)己基-2-烯酸酯、正丁基(E)-6-氧代-6-(喹啉-8-氨基)己基-2-烯酸酯、甲基(E)-5-甲基-6-氧代-6-(喹啉-8-氨基)己基-2-烯酸酯、甲基(E)-5-苯基-6-氧代-6-(喹啉-8-氨基)己基-2-烯酸酯、甲基(E)-5-苄基-6-氧代-6-(喹啉-8-氨基)己基-2-烯酸酯、(E)-6-氧代-6-(喹啉-8-基)庚基-4-烯酰胺、(E)-6-氧代-6-(喹啉-8-基)辛基-4-烯酰胺、(E)-6-氧代-6-苯基--6-(喹啉-8-基)庚基-4-烯酰胺以及(E)-氰基-N-(喹啉-8-基)戊基-4-烯酰胺中的任意一种。
5.如权利要求2所述的共轭烯烃的芳硅化合物的制备方法,其特征在于,在步骤(1)中,所述钯催化剂选自双乙腈二氯化钯、1,5-环辛二烯二氯化钯、三(二亚苄基丙酮)二钯、二氯化钯以及醋酸钯中的任意一种。
6.如权利要求2所述的共轭烯烃的芳硅化合物的制备方法,其特征在于,在步骤(1)中,所述配位化合物选自2-(二叔丁基膦)-1-(2-甲氧苯基)-1H-吡咯、2-二叔丁基磷-2-(N,N-二甲氨基)联苯、2-二叔丁基膦-1-苯基吲哚、2-二环己基膦-2'6'-双(N,N-二甲胺基)-1,1'-联苯、1-[2-(二叔丁基膦)苯基]-3,5-二苯基-1H-吡唑中的任意一种。
7.如权利要求2所述的共轭烯烃的芳硅化合物的制备方法,其特征在于,在步骤(1)中,所述硅硼键活化物选自N,N-二异丙基乙胺、N,N-二己基甲胺以及氟化钾中的任意一种。
8.如权利要求2所述的共轭烯烃的芳硅化合物的制备方法,其特征在于,在步骤(1)中,在步骤(1)中,所述溶剂选自乙腈、四氢呋喃、N,N-二甲基甲酰胺、1,2-二氯乙烷、甲苯中的任意一种。
9.如权利要求2所述的共轭烯烃的芳硅化合物的制备方法,其特征在于,在步骤(1)中,所述共轭烯烃化合物、芳基溴化物、(二甲基苯甲硅烷基)硼酸频哪醇脂、钯催化剂、配位化合物及硅硼键活化物的摩尔比为1:1.5:3:0.05:0.1:10;
在步骤(1)中,所述将反应容器置于100℃油浴中剧烈搅拌反应36小时;
在步骤(1)中,所述惰性气氛为氩气氛围;
在步骤(2)中,所述硅胶柱纯化的洗脱剂为PE:EA=15:1~5:1。
10.权利要求1或2所述的共轭烯烃的芳硅化合物的官能团转化在芳硅化合物中的应用。
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ZHEN LIU 等,: "Palladium(0)-Catalyzed Directed syn-1, 2-Carboboration and -Silylation: Alkene Scope, Applications in Dearomatization, and Stereocontrol by a Chiral Auxiliary", 《ANGEW.CHEM.INT.ED.》, vol. 58, pages 17068 - 17073 * |
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