CN111018899B - 一种金属催化末端烯烃制备1,1-炔硼类化合物的方法 - Google Patents
一种金属催化末端烯烃制备1,1-炔硼类化合物的方法 Download PDFInfo
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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
- 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
-
- 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
- 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
- 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
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
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Abstract
本发明公开了一种金属催化末端烯烃制备1,1‑炔硼类化合物的方法。在金属镍类催化剂NiA、配体和碱的作用下,将联硼酸频哪醇酯,非活化的末端烯烃与三异丙基硅基乙炔溴溶于有机溶剂中并进行反应,得到结构的1,1‑炔硼类化合物。本发明方法可高效合成上述结构的1,1‑炔硼类化合物,具有优秀的区域选择性,并且产物中含有炔烃基团与硼基团,可应用于进一步转化,从而产生各种高度官能团化的化合物。
Description
技术领域
本发明属于金属有机合成领域,一种金属催化末端烯烃1,1-炔硼化的方法及 应用。
背景技术
含有炔类化合物广泛存在于天然产物及药物分子中[a)P.J.Stang,F.Diederich,Modern Acetylene Chemistry;Wiley-VCH:Weinheim,1995;b)F. Diederich,P.J.Stang,R.R.Tykwinski,Acetylene Chemistry:Chemistry,Biology, and MaterialScience;Wiley-VCH:Weinheim,2005.]。
目前,主要合成烯烃的1,2-双官能团化[a)Z.-X.Wang,X.-Y.Bai,B.-J.Li,Synlett 2017,28,509.b)L.Fu,S.Zhou,X.Wan,P.Chen,G.Liu,J.Am.Chem.Soc. 2018,140,10965]。而目前没有文献报道由非活化的末端烯烃制备1,1-炔硼类化合 物的方法。
发明内容
本发明的目的之一在于提供一种金属催化末端烯烃1,1-炔硼化的方法,该方 法操作容易,原料便宜易得,底物范围广好,并具有很好的的区域选择性。
本发明实现上述目的之一采用以下技术方案:
一种金属催化末端烯烃制备1,1-炔硼类化合物的方法,所述1,1-炔硼类化合 物的结构式如下:
所述金属催化末端烯烃制备1,1-炔硼类化合物的方法包括以下步骤:在惰性 气体氛围下,在金属镍类催化剂NiA、配体、联硼酸频哪醇酯和碱作用下,将末 端烯烃与三异丙基硅基乙炔溴溶于有机溶剂中并进行反应,反应完全后将所得反 应混合物过滤,减压浓缩除去有机溶剂,得到1,1-炔硼类化合物,所述金属镍类 催化剂NiA:配体:联硼酸频哪醇酯:碱:末端烯烃:炔溴:有机溶剂的用量比 为摩尔:摩尔:摩尔:摩尔:摩尔:摩尔:体积mL=0.05:0.05:2:2:1:2: 2.5;
所述方法合成路线如下:
所述R1为取代的长链烷基化合物,所述的长链烷基化合物的取代基为以下 结构中的任一种或几种:卤素、芳香杂环、噻吩、呋喃、烷氧基、取代的芳基、 烷基或芳基取代的酯类。
所述上述结构式的1,1-炔硼类化合物的制备方法具体步骤如下:
在惰性气体中,将金属镍类催化剂NiA、配体、联硼酸频哪醇酯和碱溶于干 燥的有机溶剂中,然后加入末端烯烃和三异丙基硅基乙炔溴,得到反应混合物, 随后将上述反应混合物密封并从惰性气体中取出,反应完全后,过滤,减压浓缩 除去有机溶剂,得到1,1-炔硼类化合物。
所述的制备1,1-炔硼类化合物的方法,其特征在于:所述的金属镍类催化剂 NiA为Ni(NO3)·4H2O、NiBr2、NiI2、Ni(ClO4)2·6H2O、Ni(acac)2、NiBr2·DME 中的任一种。
所述的配体为如下化合物L1~L9中的任一种:
所述的碱,其阳离子为Li+、Na+、K+和Cs+中的任一种,阴离子为[CH3COO]–、[CF3COO]–、F–、CO3 2–、HCO3 –、PO4 3–、OH–、、[OMe]–和[OtBu]–中的任一种。
所述的有机溶剂为1,4-二氧六环、乙醚、甲基叔丁基醚、乙二醇二甲醚、N- 甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、二氯甲烷、 1,2-二氯乙烷、氯仿、四氯化碳、苯、甲苯、二甲苯、三甲苯、氯苯、1,2-二氯 苯、丙酮、乙腈的一种或几种。
本发明还提供由上述方法制备得到的1,1-双硼类化合物。
本发明的目的之二在于提供一种由非活化的末端烯烃制备1,1-炔硼类化合物 的方法的应用,应用于进行硼的转化,产生各种炔醇类化合物。
本发明实现目的之二采用以下技术方案:
上述1,1-炔硼类化合物用于制备炔醇类化合物中的应用,包括以下步骤:
应用的路线如下:
所述应用的具体步骤如下:
1)在惰性气体中,将金属镍类催化剂NiA、配体、联硼酸频哪醇酯和碱溶 于干燥的有机溶剂中,然后加入非活化的末端烯烃和三异丙基硅基乙炔溴,得到 反应混合物,随后将上述反应混合物密封并从惰性气体中取出,反应完全后得到 反应液Ⅰ;
2)将所述反应液Ⅰ用硅藻土过滤,然后用乙酸乙酯洗涤并浓缩,将得到的 浓缩混合物溶于四氢呋喃中,得到反应液Ⅱ,然后在0℃下,向反应液Ⅱ中加入 一定量的2M NaOH水溶液和30%H2O2溶液,然后将反应温度升至室温,并搅 拌均一,待反应结束后,用饱和Na2S2O3淬灭,再用乙酸乙酯萃取,然后合并有 机层并减压浓缩除去溶剂,再经柱层析分离纯化得到目标产物
其中,金属镍类催化剂NiA:配体:联硼酸频哪醇酯:碱:末端烯烃:炔溴: 有机溶剂:四氢呋喃:2M NaOH水溶液:30%H2O2溶液用量比为摩尔:摩尔: 摩尔:摩尔:摩尔:体积mL:体积mL:体积mL=0.05:0.05:2.0:2.0:1: 2.0:2.5:10:7.5:7.5。
与现有技术相比,本发明具有以下有益效果:
本发明公开的一种金属催化末端烯烃1,1-炔硼化的方法,使用非活化的末端 烯烃,炔溴,在金属镍催化剂作用下,一锅法反应制备1,1-炔硼类的有机化合物, 该反应方法不但可以高效的合成目标化合物,而且底物适用性强,具有良好的区 域选择性,此方法所使用的原料便宜易得,操作简便,底物官能团兼容性好,可 以高效的合成1,1-炔硼类产物。
具体实施方式
通过以下详细说明可以进一步理解本发明的特点和优点。所提供的实施例仅 是对本发明方法的说明,而不以任何方式限制本发明揭示的其余内容。
下述实施例中,是指三异丙基硅基乙炔溴结构式为B2pin2是指联硼酸频哪醇酯,结构式为 Ni(ClO4)2 6H2O是指六水合高氯酸镍化镍,L是指上述配体的一种,LiOMe是指 甲醇锂,1,4-Dioxane是指1,4-二氧六环。
实施例1
在充满氩气的手套箱中,将六水合高氯酸镍(3.7mg,0.01mmol)、配体 (L)(0.01mmol)、甲醇锂(15.0mg,0.4mmol)、联硼酸频哪醇酯(102mg, 0.4mmol),然后加入0.5mL超干的1,4-二氧六环溶剂中,然后加入庚烯(28μL, 0.2mmol)和三异丙基硅基乙炔溴(95μL,0.4mmol)将反应管密封并从手套箱 中取出,在30℃下反应12小时。反应结束后,用减压浓缩除去反应溶剂,将 得到的混合物溶于2mL四氢呋喃中,然后在0℃下,向反应液中加入1.5mL 2M 的NaOH水溶液和1.5mL 30%H2O2溶液,将反应温度升至室温,搅拌2-3小时,待反应结束后,用饱和Na2S2O3淬灭,用10mL乙酸乙酯分三次萃取,合并有机 层并减压浓缩,柱层析分离纯化得到目标产物(无色油,产率70%)。1H NMR(400 MHz,Chloroform-d)δ4.39-4.34(m,1H),1.81(d,J=5.27Hz,1H),1.73-1.62(m, 2H),1.53-1.35(m,2H),1.35-1.23(m,6H),1.11-0.98(m,21H),0.87(t,J= 6.78Hz,3H)ppm;13C NMR(101MHz,Chloroform-d)δ109.1,85.5,63.2,38.1, 31.9,29.0,25.2,22.7,18.7,14.2,11.3ppm;HRMS(ESI)Calculated for C18H36OSiNa([M+Na]+):319.2427,measured:319.2422.
实施例2
在充满氩气的手套箱中,将六水合高氯酸镍(3.7mg,0.01mmol)、配体 (L)(0.01mmol)、甲醇锂(15.0mg,0.4mmol)、联硼酸频哪醇酯(102mg, 0.4mmol),然后加入0.5mL超干的1,4-二氧六环溶剂中,然后加入6-溴-1-己烯 (26.7μL,0.2mmol)和三异丙基硅基乙炔溴(95μL,0.4mmol)将反应管密 封并从手套箱中取出,在30℃下反应12小时。反应结束后,用减压浓缩除去 反应溶剂,将得到的混合物溶于2mL四氢呋喃中,然后在0℃下,向反应液中 加入1.5mL 2M的NaOH水溶液和1.5mL 30%H2O2溶液,将反应温度升至室温, 搅拌2-3小时,待反应结束后,用饱和Na2S2O3淬灭,用10mL乙酸乙酯分三次 萃取,合并有机层并减压浓缩,柱层析分离纯化得到目标产物(无色油,产率 54%)。1H NMR(400MHz,Chloroform-d)δ4.39(t,J=6.50Hz,1H),3.40(t,J= 6.80Hz,2H),1.95(s,1H),1.90-1.83(m,2H),1.75-1.66(m,2H),1.55-1.43(m, 4H),1.10-1.00(m,21H)ppm;13C NMR(101MHz,Chloroform-d)δ108.8,85.8, 62.9,37.7,33.8,32.8,27.9,24.4,18.7,11.2ppm;HRMS(ESI)Calculated for C17H33BrOSiNa([M+Na]+):383.1376,measured:383.1373.
实施例3
在充满氩气的手套箱中,将六水合高氯酸镍(3.7mg,0.01mmol)、配体 (L)(0.01mmol)、甲醇锂(15.0mg,0.4mmol)、联硼酸频哪醇酯(102mg, 0.4mmol),然后加入0.5mL超干的1,4-二氧六环溶剂中,然后加入上述烯烃(27 mg,0.2mmol)和三异丙基硅基乙炔溴(95μL,0.4mmol)将反应管密封并从 手套箱中取出,在30℃下反应12小时。反应结束后,用减压浓缩除去反应溶 剂,将得到的混合物溶于2mL四氢呋喃中,然后在0℃下,向反应液中加入1.5mL 2M的NaOH水溶液和1.5mL 30%H2O2溶液,将反应温度升至室温,搅拌2-3 小时,待反应结束后,用饱和Na2S2O3淬灭,用10mL乙酸乙酯分三次萃取,合 并有机层并减压浓缩,柱层析分离纯化得到目标产物(无色油,产率61%)。1H NMR(400MHz,Chloroform-d)δ6.64(t,J=2.09Hz,2H),6.13(t,J=2.12Hz,2 H),4.38(t,J=6.52Hz,1H),3.88(t,J=7.13Hz,2H),1.86-1.69(m,5H),1.54- 1.47(m,2H),1.07-1.06(m,21H)ppm;13C NMR(101MHz,Chloroform-d)δ 120.6,108.6,108.1,86.0,62.8,49.6,37.5,31.4,22.6,18.7,11.2ppm;HRMS(ESI) Calculated for C20H35NOSiNa([M+Na]+):356.2380,measured:356.2380.
实施例4
在充满氩气的手套箱中,将六水合高氯酸镍(3.7mg,0.01mmol)、配体 (L)(0.01mmol)、甲醇锂(15.0mg,0.4mmol)、联硼酸频哪醇酯(102mg, 0.4mmol),然后加入0.5mL超干的1,4-二氧六环溶剂中,然后加入上述烯烃(23.7 μL,0.2mmol)和三异丙基硅基乙炔溴(95μL,0.4mmol)将反应管密封并从 手套箱中取出,在30℃下反应12小时。反应结束后,用减压浓缩除去反应溶 剂,将得到的混合物溶于2mL四氢呋喃中,然后在0℃下,向反应液中加入1.5mL 2M的NaOH水溶液和1.5mL 30%H2O2溶液,将反应温度升至室温,搅拌2-3 小时,待反应结束后,用饱和Na2S2O3淬灭,用10mL乙酸乙酯分三次萃取,合 并有机层并减压浓缩,柱层析分离纯化得到目标产物(无色油,产率48%)。1H NMR(400MHz,Chloroform-d)δ4.40(t,J=6.25Hz,1H),3.40(t,J=6.77Hz,2 H),1.94-1.87(m,3H),1.77-1.70(m,2H),1.68-1.61(m,2H),1.08-1.04(m,21 H)ppm;13C NMR(101MHz,Chloroform-d)δ108.5,86.0,62.8,37.0,33.6,32.5, 24.0,18.7,11.2ppm;HRMS(ESI)Calculated for C16H32BrOSi([M+H]+):347.1400, measured:347.1401.
实施例5
在充满氩气的手套箱中,将六水合高氯酸镍(3.7mg,0.01mmol)、配体 (L)(0.01mmol)、甲醇锂(15.0mg,0.4mmol)、联硼酸频哪醇酯(102mg, 0.4mmol),然后加入0.5mL超干的1,4-二氧六环溶剂中,然后加入上述烯烃(27.3 mg,0.2mmol)和三异丙基硅基乙炔溴(95μL,0.4mmol)将反应管密封并从 手套箱中取出,在30℃下反应12小时。反应结束后,用减压浓缩除去反应溶 剂,将得到的混合物溶于2mL四氢呋喃中,然后在0℃下,向反应液中加入1.5mL 2M的NaOH水溶液和1.5mL 30%H2O2溶液,将反应温度升至室温,搅拌2-3 小时,待反应结束后,用饱和Na2S2O3淬灭,用10mL乙酸乙酯分三次萃取,合 并有机层并减压浓缩,柱层析分离纯化得到目标产物(无色油,产率45%)。1H NMR(400MHz,Chloroform-d)δ7.28(dd,J=1.87,0.86Hz,1H),6.26(dd,J=3.18, 1.85Hz,1H),5.97(dd,J=3.13,0.93Hz,1H),4.39(t,J=6.52Hz,1H),2.64(t,J= 7.45Hz,2H),1.78-1.66(m,5H),1.58-1.50(m,2H),1.07-1.06(m,21H)ppm; 13C NMR(101MHz,Chloroform-d)δ156.2,140.9,110.2,108.9,104.9,85.7,63.0, 37.8,28.0,27.8,24.9,18.7,11.3ppm;HRMS(ESI)Calculated for C20H34O2SiNa ([M+Na]+):357.2220,measured:357.2221.
以下实施例6-实施例12均以上述实施例1-实施例5的方法步骤进行,合成 得到的化合物结构和名称、NMR与HRMS数据及产率如下表1所示:
表1实施例6~12所得化合物结构及表征
以上所述是本发明的优选实施方式而已,当然不能以此来限定本发明之权利 范围,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的 前提下,还可以做出若干改进和变动,这些改进和变动也视为本发明的保护范围。
Claims (5)
1.一种金属催化末端烯烃制备1,1-炔硼类化合物的方法,其特征在于,包括以下步骤:在惰性气体氛围下,在金属镍类催化剂NiA、配体、联硼酸频哪醇酯和碱作用下,将末端烯烃与三异丙基硅基乙炔溴溶于有机溶剂中并进行反应,反应完全后将所得反应混合物过滤,减压浓缩除去有机溶剂,得到1,1-炔硼类化合物所述金属镍类催化剂NiA:配体:联硼酸频哪醇酯:碱:末端烯烃:三异丙基硅基乙炔溴:有机溶剂的用量比为摩尔:摩尔:摩尔:摩尔:摩尔:摩尔:体积mL=0.05:0.05:2:2:1:2:2.5;
所述R1为取代的长链烷基化合物,所述的长链烷基化合物的取代基为以下结构中的任一种或几种:卤素、芳香杂环、噻吩、呋喃、烷氧基、取代的芳基、烷基或芳基取代的酯类;
所述的金属镍类催化剂NiA为Ni(NO3)·4H2O、NiBr2、NiI2、Ni(ClO4)2·6H2O、Ni(acac)2、NiBr2·DME中的任一种;
所述的配体为如下化合物L1~L9中的任一种:
所述的碱,其阳离子为Li+、Na+、K+和Cs+中的任一种,阴离子为[CH3COO]–、[CF3COO]–、F–、CO3 2–、HCO3 –、PO4 3–、OH–、、[OMe]–和[OtBu]–中的任一种。
2.如权利要求1所述的制备1,1-炔硼类化合物的方法,其特征在于:所述的有机溶剂为1,4-二氧六环、乙醚、甲基叔丁基醚、乙二醇二甲醚、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、二氯甲烷、1,2-二氯乙烷、氯仿、四氯化碳、苯、甲苯、二甲苯、三甲苯、氯苯、1,2-二氯苯、丙酮、乙腈的一种或几种。
3.一种1,1-炔硼类化合物,其特征在于,由权利要求1~2任一项方法制备得到。
5.如权利要求4所述的应用,其特征在于,所述NaOH和H2O2分别为摩尔浓度为2mol/L,质量分数为30%的水溶液,所述1,1-炔硼类化合物:四氢呋喃:2M NaOH水溶液:30%H2O2的用量比为摩尔:体积mL:体积mL:体积mL=1:10:7.5:7.5。
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