CN111484385A - 一种有机硼和无机碱催化酰胺的硅氢化反应方法 - Google Patents
一种有机硼和无机碱催化酰胺的硅氢化反应方法 Download PDFInfo
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Abstract
本发明公开了一种有机硼和无机碱催化酰胺的硅氢化反应方法,所述的酰胺包括一级酰胺、二级酰胺和三级酰胺,所述方法是以有机硼和无机碱为催化剂,以硅烷为还原剂,将一级酰胺还原为一级胺或脱水成腈,将二级酰胺还原为二级胺或醛亚胺,将三级酰胺还原为三级胺。本发明实现了酰胺的可控选择性硅氢化反应,具有操作简单、反应条件温和、底物普适性广及官能团兼容性好等优点,且反应用使用的有机硼和无机碱催化体系具有稳定性好、催化剂廉价易得、操作简便与实用性高等特点。
Description
技术领域
本发明是涉及一种酰胺的硅氢化反应方法,具体涉及一种有机硼和无机碱催化酰胺的硅氢化反应方法,属于有机合成技术领域。
背景技术
酰胺还原反应是有机合成中最重要的反应之一,该反应可以用于快速构建胺、醛及醛亚胺类骨架。目前,工业上通常采用过量的金属氢物种(如四氢锂铝和硼氢化钠等)作为还原剂实现对酰胺类底物的还原反应。尽管该金属氢物种活性高,但其存在易燃易爆等缺点,操作的危险性较高。同时该反应也存在反应条件苛刻,官能团兼容性较差及反应产生大量的废无机盐等缺点。因此,发展绿色安全环保的还原剂代替传统的金属氢物种实现酰胺的还原反应意义重大。
硅烷具有稳定性高、操作简便及毒性低等特点,因此采用硅烷作还原剂实现酰胺的还原反应吸引着化学家们的广泛关注。酰胺的硅氢化反应中除了使用硅烷做还原剂外,通常还需要使用催化剂来催化酰胺的硅氢化反应。
酰胺包括一级酰胺、二级酰胺和三级酰胺,不同类别的酰胺的还原难度不同,比如,对于一级酰胺、二级酰胺和三级酰胺这三种类型酰胺底物的硅氢化反应来说,一级酰胺的还原反应难度最大,目前一级酰胺的硅氢化反应通常得到的是腈类产物。传统的酰胺的硅氢化反应主要采用过渡金属或主族金属催化体系的催化剂来催化酰胺,但是该催化体系不仅价格昂贵,并且催化活性较差,催化的普适性较差,通常仅能还原一种或两种酰胺类底物,不适用规模化生产,例如:2001年,Igarashi和Fuchikami等人(TetrahedronLett.2001,42,1945-1947.)采用钌或锇体系与卤代烃或胺作共催化剂的情况下实现了对酰胺的硅氢化反应,该催化体系对三级和二级酰胺的硅氢化反应活性较好,但对一级酰胺的硅氢化反应活性仅能取得中等的反应活性。近年来,“无金属”的有机硼催化体系也有发展(Chem.Commun.2016,52,12195-12198;Tetrahedron Lett.2009,50,4912-4915;Chem.Commun.2014,50,9349-9352;J.Org.Chem.2014,79,7728-7733;J.Org.Chem.2016,81,4235-4243;Angew.Chem.Int.Ed.2013,52,11577-11580;Chem.Eur.J.2017,23,2005-2009;Angew.Chem.Int.Ed.2016,55,13326-13329.)。但是该催化体系通常也仅能还原一种或两种酰胺类底物,催化的普适性较差,即使能还原三种酰胺类底物,反应的催化转化数也较低,催化活性较差,不适于规模化生产。
另外,酰胺的还原产物,除了胺类产物还有亚胺类产物,其中,相比于酰胺还原为胺的反应来说,选择性地还原酰胺为亚胺的难度更大,这主要是因为亚胺的还原反应活性通常来讲要高于酰胺类底物,因此目前对酰胺的还原反应主要生成的是胺类产物,反应的可控选择性较差。目前采用催化酰胺的硅氢化反应实现酰胺到亚胺的催化转化的报道很少,目前仅有Cheng和Brookhart等人(J.Am.Chem.Soc.2012,134,11304-11307.)采用[Ir(COE)Cl]2作催化剂硅烷作还原剂实现了酰胺到亚胺的催化转化,但是其使用的[Ir(COE)Cl]2价格昂贵,不利于规模化生产。
发明内容
针对现有技术存在的上述问题,本发明的目的是提供一种有机硼和无机碱催化酰胺的硅氢化反应方法。
为实现上述发明目的,本发明采用的技术方案如下:
一种有机硼和无机碱催化酰胺的硅氢化反应方法,所述的酰胺包括一级酰胺、二级酰胺和三级酰胺,是以有机硼和无机碱为催化剂,以硅烷为还原剂,将一级酰胺还原为一级胺或脱水成腈,将二级酰胺还原为二级胺或醛亚胺,将三级酰胺还原为三级胺。
作为一种实施方案,所述的硅氢化反应,以醚(例如:甲基叔丁基醚、四氢呋喃)或者烷烃(例如:正戊烷)作溶剂。
作为一种实施方案,所述的硅氢化反应,在惰性气体(例如:氩气、氮气、氦气、氖气)气氛中反应。
作为一种实施方案,所述的硅氢化反应,反应温度为0~200℃,优选0~150℃,以25~150℃为佳。
作为一种实施方案,所述的有机硼为三烷基硼、三烷氧基硼、三芳基硼或三芳氧基硼,优选三乙基硼或三乙氧基硼。
作为一种实施方案,所述的无机碱为锂盐、钠盐、钾盐、镁盐、钙盐或铝盐类无机碱,优选氢氧化锂、氢氧化钠、氢氧化钾、甲醇钠、叔丁醇钠、叔丁醇钾、醋酸钾中的任意一种。
作为一种实施方案,有机硼和无机碱的摩尔比为1:3~3:1,优选1:1。
作为一种实施方案,催化剂的用量为酰胺的0.01~50mol%,优选1.0~10mol%。
作为一种实施方案,所述的硅烷为三取代硅烷、二取代硅烷或一取代硅烷,优选苯基硅烷或聚甲基氢硅氧烷。
作为一种实施方案,硅烷的用量为酰胺的0.1~10当量,优选1.0~5.0当量。
作为优选方案,所述的方法是以有机硼和无机碱为催化剂,以硅烷为还原剂,以醚或烷烃为溶剂,在惰性气体气氛中,于0~200℃下,将一级酰胺还原为一级胺或脱水成腈,将二级酰胺还原为二级胺或醛亚胺,将三级酰胺还原为三级胺。
作为一种实施方案,是以有机硼和无机碱为催化剂,以硅烷为还原剂,将式I结构的酰胺还原为式II-1结构的胺或式II-2结构的醛亚胺或脱水为式II-3结构的腈,具体反应式如下所示:
其中:R、R1和R2分别独立选自氢、烷基、芳基(包括取代或未取代的芳基,例如:取代或未取代的苯基)或杂环基(包括烷杂环基、芳杂环基、稠杂环基);或者,R1和R2或R一起形成饱和或不饱和的含氮杂环(包括烷基含氮杂环,R1和R形成含氮杂环时,式I结构的酰胺即相当于二级酰胺或三级酰胺中的内酰胺);且,当式I结构的酰胺被还原为式II-2结构的醛亚胺时,R2为氢;当式I结构的酰胺被脱水为式II-3结构的腈时,R1和R2均为氢,且R不为氢。
即:所述方法是以有机硼和无机碱为催化剂,以硅烷为还原剂,以醚或烷烃为溶剂,在惰性气体气氛中,于0~200℃下,将式I结构的酰胺还原为式II-1结构的胺或式II-2结构的亚胺或脱水为式II-3结构的腈。
作为优选方案,R、R1和R2分别独立选自氢、C1~C14的烷基(例如:甲基、乙基、丙基、丁基、戊基、环戊基、己基、环己基、庚基、辛基、壬基、金刚烷基、十一烷基、十二烷基、十三烷基、十四烷基)、苯基、卤代苯基、烷基取代苯基、烷氧基取代苯基、烷氨基取代苯基、苄基、五元杂环基(例如:呋喃基、噻吩基、吡咯基、噻唑基、咪唑基)、六元杂环基(例如:吡啶基、哌啶基)或稠环杂基(例如:吲哚基、喹啉基、蝶啶基、吖啶基、苯并噻吩基、苯并呋喃基),或者,R1和R2或R一起形成含氮杂五环至含氮杂九环;且,当式I结构的酰胺被还原为式II-2结构的醛亚胺时,R2为氢;当式I结构的酰胺被脱水为式II-3结构的腈时,R1和R2均为氢,且R不为氢。
一种实施方案,所述的硅氢化反应,是以有机硼和无机碱为催化剂,以硅烷为还原剂,将式I结构的酰胺还原为式II-1结构的胺,反应式为:
其中,R、R1和R2分别独立选自氢、烷基(包括C1~C14的烷基)、芳基(包括C6~C14的芳基)或杂环基(包括含氧、氮或硫的烷杂环基、芳杂环基、稠杂环基);或者,R1和R2或R一起形成饱和或不饱和的含氮杂环(包括含氮杂三环至含氮杂九环,杂环中氮原子数为1或2)。
作为优选方案,R、R1和R2分别独立选自氢、C1~C14的烷基(例如:甲基、乙基、丙基、丁基、戊基、环戊基、己基、环己基、庚基、辛基、壬基、金刚烷基、十一烷基、十二烷基、十三烷基、十四烷基)、苯基、卤代苯基、烷基取代苯基、烷氧基取代苯基、烷氨基取代苯基、苄基、五元杂环基(例如:呋喃基、噻吩基、吡咯基、噻唑基、咪唑基)、六元杂环基(例如:吡啶基、哌啶基)或稠环杂基(例如:吲哚基、喹啉基、蝶啶基、吖啶基、苯并噻吩基、苯并呋喃基),或者,R1和R2或R一起形成含氮杂五环至含氮杂九环。
作为更进一步优选方案,式I结构的酰胺选自如下化合物中的任意一种:
作为优选方案,将式I结构的酰胺还原为式II-1结构的胺的反应中,有机硼为三乙基硼,无机碱为氢氧化钠、甲醇钠或醋酸钾;还原剂为苯基硅烷,反应溶剂为醚(优选甲基叔丁基醚或四氢呋喃)或烷烃,反应温度为0~150℃。即:所述方法是以三乙基硼和无机碱(优选氢氧化钠、甲醇钠或醋酸钾)为催化剂,以苯基硅烷为还原剂,以醚(优选甲基叔丁基醚或四氢呋喃)或烷烃为溶剂,在惰性气体气氛中,于0~150℃下,将式I结构的酰胺还原为式II-1结构的胺。
另一种实施方案,所述的硅氢化反应,是以有机硼和无机碱为催化剂,以硅烷为还原剂,将式I-A结构的酰胺还原为式II-2结构的醛亚胺,反应式为:
其中,R和R1分别独立的选自烷基(包括C1~C14的烷基)、芳基(包括C6~C14的芳基)或杂环基。
作为优选方案,R和R1分别独立的选自C1~C14的烷基(例如:甲基、乙基、丙基、丁基、戊基、环戊基、己基、环己基、庚基、辛基、壬基、金刚烷基、十一烷基、十二烷基、十三烷基、十四烷基)、苯基、卤代苯基、烷基取代苯基、烷氧基取代苯基、烷氨基取代苯基、苄基、五元杂环基(例如:呋喃基、噻吩基、吡咯基、噻唑基、咪唑基)、六元杂环基(例如:吡啶基、哌啶基)或稠环杂基(例如:吲哚基、喹啉基、蝶啶基、吖啶基、苯并噻吩基、苯并呋喃基)。
作为更进一步优选方案,式I-A结构的酰胺选自如下化合物中的任意一种:
作为优选方案,将式I-A结构的酰胺还原为式II-2结构的醛亚胺的反应中,有机硼为三乙基硼,无机碱为叔丁醇钾;还原剂为苯基硅烷,反应溶剂为醚(优选四氢呋喃)或烷烃(优选正戊烷),反应温度为0~150℃。即:所述方法是以三乙基硼和叔丁醇钾为催化剂,以苯基硅烷为还原剂,以醚或烷烃为溶剂,在惰性气体气氛中,于0~150℃下,将式I-A结构的酰胺还原为式II-2结构的醛亚胺。
另一种实施方案,所述的硅氢化反应,是以有机硼和无机碱为催化剂,以硅烷为还原剂,将式I-B结构的酰胺脱水为式II-3结构的腈,反应式为:
其中:R选自烷基(包括C1~C14的烷基)、芳基(包括C6~C14的芳基)或杂环基。
作为优选方案,R选自C1~C14的烷基(例如:甲基、乙基、丙基、丁基、戊基、环戊基、己基、环己基、庚基、辛基、壬基、金刚烷基、十一烷基、十二烷基、十三烷基、十四烷基)、苯基、卤代苯基、烷基取代苯基、烷氧基取代苯基、烷氨基取代苯基、苄基、五元杂环基(例如:呋喃基、噻吩基、吡咯基、噻唑基、咪唑基)、六元杂环基(例如:吡啶基、哌啶基)或稠环杂基(例如:吲哚基、喹啉基、蝶啶基、吖啶基、苯并噻吩基、苯并呋喃基)。
作为进一步优选方案,式I-B结构的酰胺选自如下化合物中的任意一种:
作为优选方案,将式I-B结构的酰胺脱水为式II-3结构的腈的反应中,有机硼为三乙基硼,无机碱为醋酸钾;还原剂为苯基硅烷,反应溶剂为醚(优选甲基叔丁基醚),反应温度为0~150℃(优选25-100℃,以25℃为佳)。即:所述方法是以三乙基硼和醋酸钾为催化剂,以苯基硅烷为还原剂,以醚为溶剂,在惰性气体气氛中,于0~150℃下,将式I-B结构的酰胺脱水为式II-3结构的腈。
与现有技术相比,本发明具有如下显著性有益效果:
本发明以价格低廉的有机硼和无机碱为催化剂,以硅烷为还原剂,可以将一级酰胺还原为一级胺或脱水成腈,将二级酰胺还原为二级胺或醛亚胺,将三级酰胺还原为三级胺,实现了酰胺的可控选择性硅氢化反应,具有操作简单、反应条件温和、底物普适性广及官能团兼容性好等优点,且反应用使用的有机硼和无机碱催化体系具有稳定性好、催化剂廉价易得、操作简便与实用性高等特点,具有良好的工业化生产前景,适合规模化生产。
具体实施方式
下面结合具体实施例对本发明技术方案做进一步详细、完整地说明。
实施例1:将三级酰胺还原为三级胺,反应通式为:
实施例1.1
在氩气手套箱内,将NaOH(0.4mg,10.0μmol),MTBE(1.5mL)和BEt3(10.0μL,1mmol/mL in THF,10.0μmol)加入10mL封管中,并在手套箱中室温搅拌2min;随后,再依次加入三级酰胺(N,N-二甲基苯甲酰胺,149.1mg,1.0mmol)和PhSiH3(123.4μL,1.0mmol);拧紧封管,转移出手套箱,室温搅拌48小时;随后,再加入20mL稀盐酸(1mmol/mL),并在室温下搅拌6h;结束反应,用1mmol/mL的稀盐酸萃取三遍(3×10mL),合并水相,合并的水相中加入4mmol/mL的氢氧化钠水溶液(20mL),并在室温下搅拌6h;结束反应,乙醚萃取三遍(3×15mL),合并有机相,合并的有机相用饱和食盐水洗涤,无水硫酸钠干燥,过滤,浓缩得无色液体,即为所需的三级胺(133.2mg,收率为99%)。
经测试:1H NMR(300MHz,CDCl3):δ7.31(m,5H),3.42(s,2H),2.24(s,6H);
13C NMR(75MHz,CDCl3):δ138.4,128.8,127.9,126.7,64.0,45.0。
实施例1.2
经测试:1H NMR(400MHz,CDCl3):δ7.18(s,1H),7.02(d,J=8.0Hz,1H),6.71(d,J=12.0Hz,1H),4.55(t,J=8.0Hz,2H),3.48(s,2H),3.18(t,J=8.0Hz,2H),2.52(q,J=8.0Hz,4H),1.04(t,J=8.0Hz,6H);
13C NMR(101MHz,CDCl3):δ158.7,131.3,128.5,126.7,125.4,108.3,71.0,56.8,46.2,29.5,11.3;
HRMS(EI+)calcd.for[C13H19NO]:205.1467,found:205.1468。
实施例1.3
经测试:1H NMR(400MHz,CDCl3):δ7.30(dd,J=8.0,4.0Hz,2H),6.99(t,J=8.0Hz,2H),3.52(s,2H),2.51(q,J=8.0Hz,4H),1.04(t,J=8.0Hz,6H);
13C NMR(101MHz,CDCl3):δ161.6,135.39,130.1,114.6,56.5,46.4,11.5;
19F NMR(376MHz,CDCl3):δ-116.60。
实施例1.4
经测试:1H NMR(400MHz,CDCl3):δ7.44(d,J=8.0Hz,2H),7.23(d,J=8.0Hz,2H),3.52(s,2H),2.52(q,J=8.0Hz,4H),1.04(t,J=8.0Hz,6H);
13C NMR(101MHz,CDCl3):δ138.0,129.9,129.3,119.1,55.7,45.5,10.6。
实施例1.5
经测试:1H NMR(400MHz,CDCl3):δ7.63(d,J=4.0Hz,2H),7.11(d,J=8.0Hz,2H),3.50(s,2H),2.50(q,J=8.0Hz,4H),1.03(t,J=8.0Hz,6H);
13C NMR(101MHz,CDCl3):δ139.8,137.3,131.0,92.0,57.1,46.8,11.8。
实施例1.6
经测试:1H NMR(400MHz,CDCl3):δ7.22(d,J=8.0Hz,2H),7.12(d,J=8.0Hz,2H),3.54(s,2H),2.53(q,J=8.0Hz,4H),2.34(s,3H),1.05(t,J=8.0Hz,6H);
13C NMR(101MHz,CDCl3):δ136.4,136.1,128.8,128.6,57.0,46.4,20.9,11.5。
实施例1.7
经测试:1H NMR(400MHz,CDCl3):δ7.28(d,J=8.0Hz,2H),6.88(d,J=8.0Hz,2H),3.81(s,3H),3.54(s,2H),2.54(q,J=8.0Hz,4H),1.07(t,J=8.0Hz,6H);
13C NMR(101MHz,CDCl3):δ158.5,131.7,130.1,113.6,56.8,55.3,46.5,11.7。
实施例1.8
经测试:1H NMR(400MHz,CDCl3):δ7.28(d,J=8.0Hz,2H),6.88(d,J=8.0Hz,2H),3.81(s,3H),3.54(s,2H),2.54(q,J=8.0Hz,4H),1.07(t,J=8.0Hz,6H);
13C NMR(101MHz,CDCl3):δ158.5,131.7,130.1,113.6,56.8,55.3,46.5,11.7。
实施例1.9
经测试:1H NMR(400MHz,CDCl3):δ7.20(m,3H),7.08(d,J=8.0Hz,1H),3.56(s,2H),2.56(q,J=8.0Hz,4H),2.38(s,3H),1.08(t,J=8.0Hz,6H);
13C NMR(101MHz,CDCl3):δ139.6,137.5,129.4,127.7,127.2,125.8,57.2,46.5,21.2,11.4。
实施例1.10
经测试:1H NMR(400MHz,CDCl3):δ7.35(s,1H),6.29(t,J=4.0Hz,1H),6.16(d,J=4.0Hz,1H),3.64(s,2H),2.51(q,J=8.0Hz,4H),1.06(t,J=8.0Hz,6H);
13C NMR(101MHz,CDCl3):δ152.2,141.6,109.7,108.1,48.6,46.6,11.6。
实施例1.11
经测试:1H NMR(400MHz,CDCl3)δ7.21(dd,J=4.0Hz,1H),6.96(dd,J=4.0Hz,1H),6.90(m,1H),3.83(s,2H),2.55(q,J=8.0Hz,4H),1.08(t,J=8.0Hz,6H);
13C NMR(101MHz,CDCl3):δ142.6,126.1,125.3,124.3,51.1,46.3,11.7;
HRMS(EI+)calcd.for[C9H15NS]:169.0925,found:169.0919。
实施例1.12
经测试:1H NMR(300MHz,CDCl3):δ7.26(t,J=8.0Hz,2H),6.72(m,3H),3.43(q,J=8.0Hz,2H),2.93(s,3H),1.14(t,J=8.0Hz,3H);
13C NMR(75MHz,CDCl3):δ148.6,128.7,11520.6,111.9,46.4,37.0,10.7。
实施例1.13
经测试:1H NMR(300MHz,CDCl3):δ2.18(s,6H),1.42(m,2H),1.25(m,12H),0.85(t,J=8.0Hz,3H);
13C NMR(75MHz,CDCl3):δ59.7,45.2,31.6,29.3,29.0,27.5,27.2,22.4,13.8。
实施例2:将二级酰胺还原为二级胺,反应通式为:
实施例2.1
在氩气手套箱内,将NaOMe(1.4mg,25.0μmol),THF(1.5mL)和BEt3(25.0μL,1mmol/mL in THF,25.0μmol)加入10mL封管中,并在手套箱中室温搅拌2min;随后,再依次加入二级酰胺(N-甲基苯甲酰胺,135.1mg,1.0mmol)和PhSiH3(246.8μL,2.0mmol);拧紧封管,转移出手套箱,50℃下搅拌48小时;随后,再加入20mL稀盐酸(1mmol/mL),并在室温下搅拌6h;结束反应,用1mmol/mL的稀盐酸萃取三遍(3×10mL),合并水相,合并的水相加入4mmol/mL的氢氧化钠水溶液(20mL),并在室温下搅拌6h;结束反应,乙醚萃取三遍(3×15mL),合并有机相,合并的有机相用饱和食盐水洗涤,无水硫酸钠干燥,过滤,浓缩得无色液体,即得所需的二级胺(114.7mg,收率为95%)。
经测试:1H NMR(400MHz,CDCl3):δ7.32(m,4H),7.25(m,1H),3.75(s,2H),2.46(s,3H),1.38(s,1H);
13C NMR(101MHz,CDCl3):δ140.2,128.4,128.2,126.9,56.1,36.0。
实施例2.2
经测试:1H NMR(400MHz,CDCl3):δ7.32(d,J=4.0Hz,4H),7.24(m,1H),3.82(s,2H),2.50(s,1H),1.92(d,J=12.0Hz,2H),1.74(m,2H),1.62(m,2H),1.20(m,5H);
13C NMR(101MHz,CDCl3):δ140.9,128.5,128.2,126.9,56.3,51.1,33.6,26.3,25.1。
实施例2.3
经测试:1H NMR(400MHz,CDCl3):δ7.39(m,4H),7.31(m,1H),7.21(t,J=8.0Hz,2H),6.75(t,J=8.0Hz,1H),6.67(d,J=8.0Hz,2H),4.36(s,2H),4.05(bs,1H);
13C NMR(101MHz,CDCl3):δ148.2,139.5,129.4,128.8,127.6,127.3,117.7,113.0,48.4。
实施例2.4
经测试:1H NMR(400MHz,CDCl3):δ7.32(m,4H),7.26(m,1H),3.80(s,2H),2.69(q,J=8.0Hz,2H),1.38(bs,1H),1.15(t,J=8.0Hz,3H);
13C NMR(101MHz,CDCl3):δ140.6,128.4,128.2,126.9,54.1,43.7,15.4。
实施例2.5
经测试:1H NMR(400MHz,CDCl3):δ7.31(t,J=8.0Hz,2H),6.73(t,J=8.0Hz,1H),6.64(d,J=8.0Hz,2H),3.58(bs,1H),3.13(t,J=8.0Hz,2H),1.65(m,2H),1.40(m,22H),0.94(t,J=8.0Hz,3H);
13C NMR(101MHz,CDCl3):δ148.6,129.3,117.2,112.8,44.1,32.1,29.8,29.8,29.8,29.8,29.8,29.8,29.7,29.6,29.5,27.3,22.8,14.3。
实施例2.6
经测试:1H NMR(400MHz,CDCl3):δ6.80(m,2H),6.69(t,J=8.0Hz,1H),6.61(d,J=8.0Hz,1H),4.26(t,J=8.0Hz,2H),3.76(bs,1H),3.41(t,J=8.0Hz,2H);
13C NMR(101MHz,CDCl3):δ144.1,133.7,121.3,118.8,116.8,115.7,65.2,41.0。
实施例3:将一级酰胺还原为一级胺,反应通式为:
实施例3.1
在氩气手套箱内,将KOAc(2.0mg,20.0μmol),MTBE(1.5mL)和BEt3(20.0μL,1mmol/mL in THF,20.0μmol)加入10mL封管中,并在手套箱中室温搅拌2min;随后,再依次加入一级酰胺(苯甲酰胺,24.2mg,0.2mmol)和PhSiH3(49.4μL,0.4mmol);拧紧封管,转移出手套箱,80℃下搅拌24小时;随后,再加入2mL HCl/EA(2mmol/mL的乙酸乙酯溶液),并在室温下搅拌8h;结束反应,过滤,二氯甲烷洗涤,浓缩得白色固体,即得所需的一级胺(21.6mg,收率为76%)。
经测试:1H NMR(400MHz,DMSO-d6):δ8.34(bs,3H),7.47(s,2H),7.38(m,3H),3.98(s,2H);
13C NMR(101MHz,DMSO-d6):δ134.2,129.0,128.5,128.4,42.1。
实施例3.2
经测试:1H NMR(400MHz,DMSO-d6):δ8.63(bs,3H),7.54(s,2H),7.20(s,2H),3.93(s,2H);
13C NMR(101MHz,DMSO-d6):δ162.1,131.4,130.4,115.3,41.3;
19F NMR(376MHz,CDCl3):δ-109.1。
实施例3.3
经测试:1H NMR(400MHz,DMSO-d6):δ8.60(bs,3H),7.53(d,J=8.0Hz,2H),7.45(d,J=8.0Hz,2H),3.98(s,2H);
13C NMR(101MHz,DMSO-d6):δ133.2,131.1,128.6。
实施例3.4
经测试:1H NMR(400MHz,DMSO-d6):δ8.67(s,3H),7.58(s,2H),7.48(s,2H),3.97(s,2H);
13C NMR(101MHz,DMSO-d6):δ133.5,131.3,121.6,41.4。
实施例3.5
经测试:1H NMR(400MHz,DMSO-d6):δ8.54(bs,3H),7.46(s,2H),6.96(s,2H),3.90(s,3H),3.76(s,3H);
13C NMR(101MHz,DMSO-d6):δ159.3,130.6,126.2,113.9,55.2,41.6。
实施例3.6
经测试:1H NMR(400MHz,DMSO-d6):δ8.55(s,3H),7.29(s,3H),7.17(s,1H),3.93(s,2H),2.30(s,3H);
13C NMR(101MHz,DMSO-d6):δ137.6,134.0,129.5,128.9,128.4,125.9,42.1,20.9。
实施例3.7
经测试:1H NMR(400MHz,DMSO-d6):δ8.76(s,3H),8.11(s,1H),7.95(s,2H),7.58(s,4H),4.47(s,2H);
13C NMR(101MHz,DMSO-d6):δ133.0,130.5,129.8,128.8,128.5,127.1,126.6,126.0,125.2,123.3,38.9。
实施例3.8
经测试:1H NMR(400MHz,DMSO-d6):δ8.88(bs,3H),7.98(d,J=8.0Hz,1H),7.85(d,J=8.0Hz,1H),7.59(s,1H),7.38(m,2H),4.32(s,2H);
13C NMR(101MHz,DMSO-d6):δ139.6,138.9,136.7,125.3,124.8,124.6,123.7,122.5,37.4。
实施例3.9
经测试:1H NMR(400MHz,DMSO-d6):δ7.95(s,3H),7.26(s,5H),2.94(s,3H);
13C NMR(101MHz,DMSO-d6):δ137.6,128.7,128.6,126.7,40.0,33.0。
实施例3.10
经测试:1H NMR(400MHz,DMSO-d6):δ8.15(s,3H),2.57(s,2H),1.68(m,6H),1.13(s,3H),0.89(s,2H);
13C NMR(101MHz,DMSO-d6):δ44.3,35.4,29.8,25.7,25.1。
实施例3.11
经测试:1H NMR(400MHz,DMSO-d6):δ7.90(s,3H),2.43(s,2H),1.93(s,3H),1.66(d,J=12.0Hz,3H),1.56(d,J=12.0Hz,3H),1.49(s,6H);
13C NMR(101MHz,DMSO-d6):δ50.0,38.9,36.1,31.6,27.4。
实施例4:将二级酰胺还原为醛亚胺,反应通式为:
实施例4.1
在氩气手套箱内,将KOtBu(1.0mg,9.0μmol),THF(1.5mL)和BEt3(9.0μL,1mmol/mLin THF,9.0μmol)加入10mL封管中,并在手套箱中室温搅拌2min;随后,再依次加入二级酰胺(N-环己基苯甲酰胺,73.1mg,0.36mmol)和PhSiH3(88.8μL,0.72mmol);拧紧封管,转移出手套箱,80℃下搅拌36小时,结束反应,浓缩,库克勒蒸馏,得无色液体,即得所需的醛亚胺(67.0mg,收率为99%)。
经测试:1H NMR(400MHz,CDCl3):δ8.32(s,1H),7.74(d,J=8.0Hz,2H),7.40(d,J=8.0Hz,3H),3.20(m,1H),1.85(m,2H),1.67(m,5H),1.33(m,3H);
13C NMR(101MHz,CDCl3):δ158.4,136.3,130.1,128.3,127.8,69.8,34.1,25.4,24.6。
实施例4.2
经测试:1H NMR(400MHz,CDCl3):δ8.29(s,1H),7.62(d,J=8.0Hz,2H),7.20(d,J=8.0Hz,2H),3.17(m,1H),2.37(s,3H),1.84(m,2H),1.65(m,5H),1.32(m,3H);
13C NMR(101MHz,CDCl3):δ158.3,140.3,133.7,129.0,127.8,69.8,34.2,25.4,24.7,21.2。
实施例4.3
经测试:1H NMR(400MHz,CDCl3):δ8.25(s,1H),7.68(d,J=8.0Hz,2H),6.92(d,J=8.0Hz,2H),3.83(s,3H),3.15(m,1H),1.83(m,2H),1.65(m,5H),1.32(m,3H);
13C NMR(101MHz,CDCl3):δ161.1,157.8,129.3,129.3,113.6,69.8,55.1,34.2,25.4,24.7。
实施例4.4
经测试:1H NMR(400MHz,CDCl3):δ8.27(s,1H),7.72(dd,J=8.0,4.0Hz,2H),7.07(t,J=8.0Hz,2H),3.18(m,1H),1.79(m,2H),1.70(m,3H),1.57(m,2H),1.30(m,3H);
13C NMR(101MHz,CDCl3):δ157.2,129.9,129.8,115.6,115.4,69.9,34.3,25.6,24.8.19F NMR(376MHz,CDCl3):δ-110.2。
实施例5:将一级酰胺脱水为腈,反应通式为:
实施例5.1
在氩气手套箱内,将KOAc(5.0mg,50.0μmol),MTBE(1.5mL)和BEt3(50.0μL,1mmol/mL in THF,50.0μmol)加入10mL封管中,并在手套箱中室温搅拌2min;随后,再依次加入一级酰胺(苯甲酰胺,121.2mg,1.0mmol)和PhSiH3(246.8μL,2.0mmol);拧紧封管,转移出手套箱,室温下搅拌48小时;结束反应,浓缩,柱层析得无色液体,即得所需的腈(91.6mg,收率为89%)。
经测试:1H NMR(400MHz,CDCl3):δ7.62-7.55(m,3H),7.44(t,J=8.0Hz,2H);
13C NMR(101MHz,CDCl3):δ132.8,132.0,129.1,118.8,112.3。
实施例5.2
经测试:1H NMR(400MHz,CDCl3):δ7.53(d,J=8.0Hz,2H),7.26(d,J=8.0Hz,2H),2.41(s,3H);
13C NMR(101MHz,CDCl3):δ143.8,132.1,129.9,119.3,109.4,22.0。
实施例5.3
经测试:1H NMR(400MHz,CDCl3):δ7.58(d,J=12.0Hz,2H),6.94(d,J=8.0Hz,2H),3.85(s,3H);
13C NMR(101MHz,CDCl3):δ162.9,134.0,119.3,114.8,103.9,55.6。
实施例5.4
经测试:1H NMR(400MHz,CDCl3):δ7.68(m,2H),7.17(m,2H);
19F NMR(376MHz,CDCl3):δ-102.4;
13C NMR(101MHz,CDCl3):δ165.1,134.8,118.3,117.0,108.6.。
实施例5.5
经测试:1H NMR(400MHz,CDCl3):δ7.60(d,J=8.0Hz,2H),7.46(d,J=8.0Hz,2H);
13C NMR(101MHz,CDCl3):δ139.6,133.5,129.8,118.1,110.8。
实施例5.6
经测试:1H NMR(400MHz,CDCl3):δ7.63(d,J=8.0Hz,2H),7.52(d,J=8.0Hz,2H);
13C NMR(101MHz,CDCl3):δ133.5,132.8,128.1,118.2,111.3。
实施例5.7
经测试:1H NMR(400MHz,CDCl3):δ7.46(s,2H),7.40(d,J=4.0Hz,1H),7.35(t,J=8.0Hz,1H),2.39(s,3H).;
13C NMR(101MHz,CDCl3):δ139.3,133.8,132.6,129.4,129.1,119.2,112.3,21.3。
实施例5.8
经测试:1H NMR(400MHz,CDCl3):δ7.54(d,J=8.0Hz,2H),6.99(m,2H),3.92(s,3H);
13C NMR(101MHz,CDCl3):δ161.3,134.5,133.8,120.8,116.6,111.4,101.8,56.1。
实施例5.9
经测试:1H NMR(400MHz,CDCl3):δ8.24(d,J=8.0Hz,1H),8.09(d,J=8.0Hz,1H),7.92(m,2H),7.70(m,1H),7.63(m,1H),7.53(m,1H);
13C NMR(101MHz,CDCl3):δ133.4,133.0,132.8,132.5,128.8,128.7,127.7,125.3,125.0,118.0,110.3。
实施例5.10
经测试:1H NMR(400MHz,CDCl3):δ7.89(m,3H),7.54(t,J=8.0Hz,1H),7.48(t,J=8.0Hz,1H);
13C NMR(101MHz,CDCl3):δ141.4,137.5,135.1,128.0,125.8,125.4,122.5,114.6,109.8。
实施例5.11
经测试:1H NMR(400MHz,CDCl3):δ7.60(m,2H),7.12(m,1H);
13C NMR(101MHz,CDCl3):δ137.4,132.7,127.7,114.3,109.7。
实施例5.12
经测试:1H NMR(400MHz,CDCl3):δ7.37(m,5H),3.73(s,2H);
13C NMR(101MHz,CDCl3):δ130.0,129.1,128.0,127.9,118.0,23.6。
最后需要在此指出的是:以上仅是本发明的部分优选实施例,不能理解为对本发明保护范围的限制,本领域的技术人员根据本发明的上述内容做出的一些非本质的改进和调整均属于本发明的保护范围。
Claims (9)
1.一种有机硼和无机碱催化酰胺的硅氢化反应方法,所述的酰胺包括一级酰胺、二级酰胺和三级酰胺,其特征在于:是以有机硼和无机碱为催化剂,以硅烷为还原剂,将一级酰胺还原为一级胺或脱水成腈,将二级酰胺还原为二级胺或醛亚胺,将三级酰胺还原为三级胺。
2.根据权利要求1所述的硅氢化反应方法,其特征在于:所述的有机硼为三烷基硼、三烷氧基硼、三芳基硼或三芳氧基硼。
3.根据权利要求1所述的硅氢化反应方法,其特征在于:所述的无机碱为锂盐、钠盐、钾盐、镁盐、钙盐或铝盐类无机碱。
4.根据权利要求1所述的硅氢化反应方法,其特征在于:所述的硅烷为三取代硅烷、二取代硅烷或一取代硅烷。
7.根据权利要求6所述的硅氢化反应方法,其特征在于:R、R1和R2分别独立选自氢、C1~C14的烷基、苯基、卤代苯基、烷基取代苯基、烷氧基取代苯基、烷氨基取代苯基、苄基、五元杂环基、六元杂环基或稠环杂基,或者,R1和R2或R一起形成含氮杂五环至含氮杂九环。
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CN114181090A (zh) * | 2020-09-15 | 2022-03-15 | 厦门大学 | 由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法 |
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CN114181090A (zh) * | 2020-09-15 | 2022-03-15 | 厦门大学 | 由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法 |
CN114181090B (zh) * | 2020-09-15 | 2023-04-28 | 厦门大学 | 由酰胺经铱和硼试剂共同催化硅氢化合成胺类化合物的制备方法 |
CN112661667A (zh) * | 2020-12-28 | 2021-04-16 | 浦拉司科技(上海)有限责任公司 | 一种三氟乙脒的制备方法 |
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