CN111138283B - 苯并恶唑连接的共价有机框架不对称光催化制备手性醛化合物的方法 - Google Patents
苯并恶唑连接的共价有机框架不对称光催化制备手性醛化合物的方法 Download PDFInfo
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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Abstract
本发明公开了苯并恶唑连接的共价有机框架不对称光催化制备手性醛化合物的方法。该方法通过苯并恶唑连接的共价有机框架不对称光催化制备手性醛化合物,以醛和烷基溴代物为底物,苯并恶唑连接的共价有机框架为光催化剂,加入咪唑啉酮类的手性催化剂、溶剂以及碱,在氩气氛围中室温下可见光光照条件下搅拌反应,合成手性醛化合物。苯并恶唑连接的共价有机框架是一种不含金属元素且可以吸收可见光的晶型有机多孔聚合物光催化剂,具有比表面积高,晶型好,化学稳定性和光稳定性好,合适的禁带宽度,易于分离和回收等优点。将该催化剂用于合成手性醛类化合物,反应过程操作简单,在可见光下进行,条件温和,催化效果好,便于分离,可以循环使用。
Description
技术领域
本发明属于光催化有机合成和功能材料技术领域,具体涉及一种苯并恶唑连接的共价有机框架不对称光催化制备手性醛化合物的方法。
背景技术
手性醛化合物在医药和生物领域发挥着重要的作用,而如何高效地获得手性醛化合物一直以来都是化学工作者致力解决的关键科学问题。近年来,通过不对称光催化获得手性醛化合物引起了科学家的广泛关注。不对称光催化有操作简单,绿色节能,反应条件温和等优点。MacMillan在2008年报道了可见光促进的醛的不对称烷基化反应,针对该反应,目前用到的光催化剂大多都是金属复合物或者有机染料,这些光催化剂由于其价格昂贵,成本高,不稳定,难于分离和回收等缺点限制了他们的实际使用。因此,发展一种高效,易于分离并可回收的不对称光催化方法制备手性醛化合物具有重要意义。
发明内容
本发明的目的在于克服现有技术的不足,提供一种高效,易于分离回收的苯并恶唑连接的共价有机框架不对称光催化制备手性醛化合物的方法。
为了实现上述发明目的,本发明采用以下技术方案:
1.光催化剂苯并恶唑连接的共价有机框架材料LZU-190的合成:将前体1,3,5-三甲酰苯和2,5-二羟基-1,4-对苯二胺盐酸盐,苯并咪唑混合均匀,加入组合溶剂N-甲基吡咯烷酮和均三甲苯,反应在185℃下进行。反应在密封的反应器中发生,反应时间为五天。离心洗涤干燥即可得到苯并恶唑连接的共价有机框架材料LZU-190。
2.手性醛化合物的制备:在反应容器中,加入底物醛和烷基溴代物,苯并恶唑连接的共价有机框架材料LZU-190光催化剂,手性咪唑啉酮催化剂,溶剂和碱,室温下用可见光照射反应24小时,反应结束后,离心分离光催化剂LZU-190,用乙酸乙酯,丙酮,乙醇洗涤,收集清液并旋干,经柱层析分离得到目标产物,产物的对映选择性通过液体核磁氢谱或者高效液相色谱仪测试。其反应式如下:
进一步地,所述有机催化剂为手性咪唑啉酮类催化剂。
进一步地,所述的溶剂为乙腈,四氢呋喃,甲醇,N,N-二甲基甲酰胺,二氯甲烷或二甲基亚砜中的一种。
进一步地,所述的碱为碳酸氢钠,碳酸钾,2,6-二甲基吡啶或三乙胺中的一种。
进一步地,所述苯并噁唑连接的共价有机框架LZU-190与底物的摩尔比为1:5-10。
进一步地,所述手性咪唑啉酮类催化剂与底物的摩尔比为1:3-10。
进一步地,通过离心分离LZU-190,用乙酸乙酯,丙酮,乙醇洗涤,收集清液,旋干,经柱层析得到目标产物。
进一步地,所述的柱层析是以石油醚和乙酸乙酯体积比5-50:1的混合溶剂为洗脱剂进行柱层析提纯。
进一步地,所得产物通过和手性醇化合物生成缩醛,然后用液体核磁氢谱检测或者直接用液相色谱仪检测。
本发明的原理为在可见光照射下,苯并恶唑连接的共价有机框架LZU-190作为光催化剂和手性咪唑啉酮催化剂组成双催化体系,协同实现可见光驱动的醛的不对称烷基化反应合成手性醛化合物。
与现有技术相比,本发明的有益效果:
1)本发明的合成方法避免了有毒有害并且昂贵的金属复合物的使用,反应条件温和,操作简单。
2)本发明的合成方法易于分离光催化剂,达到重复使用的目的。具有较大的工业应用潜力。
3)本发明中在检测条件为用手性IC柱,正己烷/异丙醇为90/10,流速为1mL/min,检测波长为209nm时,保留时间为19.71-24.94min,检测波长为216nm时,保留时间16.25-19.77min,检测波长越大,其保留的时间越短。
4)本发明中手性醛化合物的产率为53%~58%,对映体过量百分数为80%~87%,说明手性醛化合物具有较高的对映体过量,催化性能好,结构稳定,能够使得反应选择性增加。
附图说明
附图用来提供对本发明的进一步理解,并且构成说明书的一部分,与本发明的实施例起用于解释本发明,并不构成对本发明的限制。在附图中:
图1是本发明所合成的苯并恶唑连接的共价有机框架材料LZU-190的粉末X射线衍射图谱。
图2是本发明所合成的苯并恶唑连接的共价有机框架材料LZU-190的固体核磁图谱。其中a是NQSMAS图谱,b是13CCP/MAS图谱。
图3是本发明所合成的苯并恶唑连接的共价有机框架材料LZU-190氮气吸脱附曲线和孔径分布图谱。
图4是本发明的不对称光催化反应示意图。
具体实施方式
下面结合附图和实施例,对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明,但不用来限制本发明的范围。
本发明中光催化剂LZU-190的合成方法为:将前体1,3,5-三甲酰苯和2,5-二羟基-1,4-对苯二胺盐酸盐按摩尔比2:3混合,加入3当量的苯并咪唑混合均匀,加入组合溶剂N-甲基吡咯烷酮和均三甲苯,反应在185℃下进行。反应在密封的反应器中发生,反应时间为五天。离心洗涤干燥即可得到苯并恶唑连接的共价有机框架材料LZU-190。
实施例1
在反应容器中,加入125μL的正辛醛,68μL的溴代丙二酸二乙酯,91μL的2,6-二甲基吡啶,0.2当量的LZU-190,0.25当量的有机催化剂,0.8mL的DME,氩气保护,可见光照射,室温搅拌24小时,反应结束后离心洗涤分离LZU-190,旋干清液,用柱层析洗脱液位体积比为50:1的石油醚与乙酸乙酯混合溶剂,产率为55%,对映选择性用手性二醇化合物和产物反应得到缩醛产物,通过液体核磁氢谱得到ee值为84%。
产物:
Colorless oil,yield:55%,ee:84%.
1HNMR(400MHz,CDCl3)δ9.76(d,J=0.4Hz,1H,CHO),4.24-4.16(m,4H,2×COCH2CH3),3.74(d,J=8.6Hz,1H,CH(CO2Et)2),3.08-3.11(m,1H,HCOCH),1.74-1.65(m,1H,CH2(CH2)4CH3),1.61-1.53(m,1H,CH2(CH2)4CH3),1.29-1.23(m,14H,CH2(CH2)4CH3,2×CO2CH2CH3),0.86(t,J=6.6Hz,3H,CO2CH2CH3).
13CNMR(100MHz,CDCl3)δ201.7,168.3,168.2,61.9,61.9,51.9,50.3,31.4,29.4,27.2,26.6,22.6,14.2,14.1,13.1.
实施例2
在反应容器中,加入105μL的苯丙醛,68μL的溴代丙二酸二乙酯,91μL的2,6-二甲基吡啶,0.2当量的LZU-190,0.25当量的有机催化剂,0.8mL的DME,氩气保护,可见光照射,室温搅拌12小时,反应结束后离心洗涤分离LZU-190,旋干清液,用柱层析洗脱液位体积比为50:1的石油醚与乙酸乙酯混合溶剂,产率为45%,对映选择性用手性二醇化合物和产物反应得到缩醛产物,通过液体核磁氢谱得到ee值为65%。
产物
Colorlessoil,yield:45%,ee:65%.
1HNMR(400MHz,CDCl3)δ9.84(d,J=0.4Hz,1H,CHO),7.39-7.24(m,5H,ArH),4.30-4.23(m,4H,2×COCH2CH3),3.75(d,J=7.0Hz,1H,CH(CO2Et)2),3.48(q,J=7.4Hz,1H,HCOCH),3.12(dd,J=14.2,7.5Hz,1H,CH2Ph),2.83(dd,J=14.2,7.3Hz,1H,CH2Ph),1.27(t,J=7.1Hz,6H,2×CO2CH2CH3).
13CNMR(100MHz,CDCl3)δ201.3,168.2,168.1,137.5,129.3,128.9,127.1,62.1,62.0,51.9,51.6,33.3,14.1.
实例3
在反应容器中,加入105μL的苯丙醛,53μL的溴代丙二酸二甲酯,91μL的2,6-二甲基吡啶,0.2当量的LZU-190,0.25当量的有机催化剂,0.8mL的DME,氩气保护,可见光照射,室温搅拌8小时,反应结束后离心洗涤分离LZU-190,旋干清液,用柱层析洗脱液位体积比为50:1的石油醚与乙酸乙酯混合溶剂,产率为34%,对映选择性用手性二醇化合物和产物反应得到缩醛产物,通过液体核磁氢谱得到ee值为47%。
产物
Colorlessoil,yield:34%,ee:47%.
1HNMR(400MHz,CDCl3)δ9.83(d,J=0.3Hz,1H,CHO),7.40-7.24(m,5H,ArH),3.81(s,3H,CO2CH3),3.80(s,3H,CO2CH3),3.79(d,J=8.0Hz,1H,CH(CO2CH3)2),3.51-3.46(m,1H,HCOCH),3.21(dd,J=14.2,7.5Hz,1H,PhCH2),2.93(dd,J=14.2,7.3Hz,1H,PhCH2).
13CNMR(100MHz,CDCl3)δ201.1,168.6,168.5,137.3,129.2,128.9,127.1,53.0,53.0,52.0,51.1,33.3.
对映选择性用高效液相色谱仪HPLC测得。检测条件为用手性IC柱,正己烷/异丙醇为90/10,流速为1mL/min,检测波长为209nm,保留时间tmajor=19.71min,tminor=24.94min。
实例4
在反应容器中,加入105μL的苯丙醛,68μL的2-溴苯乙酮,91μL的2,6-二甲基吡啶,0.2当量的LZU-190,0.25当量的有机催化剂,0.8mL的DME,氩气保护,可见光照射,室温搅拌4天,反应结束后离心洗涤分离LZU-190,旋干清液,用柱层析洗脱液位体积比为50:1的石油醚与乙酸乙酯混合溶剂,产率为14%,对映选择性用用高效液相色谱仪测得ee值为64%。
产物
Colorless oil,yield:14%,ee:64%.
1HNMR(400MHz,CDCl3)δ9.90(d,J=0.7Hz,1H,CHO),7.95-7.85(dd,J=7.4Hz,2H,ArH),7.58-7.54(m,1H,ArH),7.51-7.43(m,2H,ArH),7.32-7.28(m,2H,ArH),7.25-7.19(m,3H,ArH),3.47-3.37(m,2H,PhCOCH2),3.20-3.15(m,1H,CHOCH),3.05-2.98(m,1H,PhCH2),2.86-2.80(m,1H,PhCH2).
13CNMR(100MHz,CDCl3)δ203.1,198.0,138.3,136.3,133.5,129.2,128.9,128.8,128.3,128.3,126.7,48.5,37.4,34.9.
对映选择性用高效液相色谱仪HPLC测得。检测条件为用手性IC柱,正己烷/异丙醇为90/10,流速为1mL/min,检测波长为216nm,保留时间tmajor=19.77min,tminor=16.25min。
实例5
在反应容器中,加入133μL的顺-6-壬烯醛,68μL的溴代丙二酸二乙酯,91μL的2,6-二甲基吡啶,0.2当量的LZU-190,0.25当量的有机催化剂,0.8mL的DME,氩气保护,可见光照射,室温搅拌46小时,反应结束后离心洗涤分离LZU-190,旋干清液,用柱层析洗脱液位体积比为50:1的石油醚与乙酸乙酯混合溶剂,产率为47%,对映选择性用手性二醇化合物和产物反应得到缩醛产物,通过液体核磁氢谱得到ee值为78%。
产物
Colorlessoil,yield:47%,ee:78%.
1HNMR(400MHz,CDCl3)δ9.75(d,J=1.0Hz,1H,CHO),5.38-5.34(m,1H,CH2CHCHCH2),5.27-5.22(m,1H,CH2CHCHCH2),4.24-4.15(m,4H,2×CO2CH2CH3),3.73(d,J=8.5Hz,1H,CH(CO2Et)2),3.12(dddd,J=0.8,5.1,8.8,8.8Hz,1H,HCOCH),2.05-1.96(m,4H,CH2CHCHCH2),1.71-1.65(m,1H,CH2CH2CH2CHCHCH2CH3),1.61-1.55(m,1H,CH2CH2CH2CHCHCH2CH3),1.47-1.41(m,2H,CH2CH2CH2CHCHCH2CH3),1.28(t,J=7.2Hz,3H,CO2CH2CH3),1.26(t,J=7.1Hz,3H,CO2CH2CH3),0.95(t,J=8.0Hz,3H,CH2CH2CH2CHCHCH2CH3).
13C NMR(100MHz,CDCl3)δ201.5,168.2,168.1,132.7,127.9,61.9,61.9,51.8,50.3,27.0,26.7,26.7,20.6,14.4,14.1,14.1.
实例6
在反应容器中,加入182mg的4-(2-氧代乙基)哌啶-1-羧酸叔丁酯,68μL的溴代丙二酸二乙酯,91μL的2,6-二甲基吡啶,0.2当量的LZU-190,0.25当量的有机催化剂,0.8mL的DME,氩气保护,可见光照射,室温搅拌46小时,反应结束后离心洗涤分离LZU-190,旋干清液,用柱层析洗脱液位体积比为50:1的石油醚与乙酸乙酯混合溶剂,产率为48%,对映选择性用用高效液相色谱仪测得ee值为78%。
产物
Colorless oil,yield:48%,ee:78%.
1HNMR(400MHz,CDCl3)δ9.82(d,J=0.9Hz,1H,CHO),4.26-4.12(m,6H,2×CO2CH2CH3&CH2NBoc),3.83(d,J=9.0Hz,1H,CH(CO2Et)2),3.15(dd,J=5.0,9.0Hz,1H,HCOCH),2.61(br s,2H,CH2NBoc),1.87-1.78(m,1H,CH(CH2)2NBoc)1.75-1.66(m,2H,CH2CH2NBoc),1.43-1.42(m,11H,CH2CH2NBoc&C(CH3)3,1.28-1.22(m,6H,2×CO2CH2CH3).
13CNMR(100MHz,CDCl3)δ201.3,168.4,168.1,154.7,79.8,62.1,62.1,54.8,50.4,50.2,35.9,30.0,28.5,14.2,14.1.
实例7
本发明所述的光催化剂具有可回收重复使用的优势,具体操作如下:
在反应容器中,加入125μL的正辛醛,68μL的溴代丙二酸二乙酯,91μL的2,6-二甲基吡啶,0.2当量的LZU-190,0.25当量的有机催化剂,0.8mL的DME,氩气保护,可见光照射,室温搅拌24小时,反应结束后离心洗涤分离LZU-190,旋干清液,用柱层析洗脱液位体积比为50:1的石油醚与乙酸乙酯混合溶剂提纯的目标产物。所分离回收的光催化剂LZU-190可以投入下一次循环实验,具体操作同上。光催化剂LZU-190可以重复使用5次,活性和选择性都能保持。
实验例1:在实施例3和实施例4中,高效液相色谱仪HPLC进行色谱测验,检测条件为用手性IC柱,正己烷/异丙醇为90/10,具体如表1所示:
由表1可知,本发明中在检测条件为用手性IC柱,正己烷/异丙醇为90/10,流速为1mL/min,检测波长为209nm时,保留时间为19.71-24.94min,检测波长为216nm时,保留时间16.25-19.77min,检测波长越大,其保留的时间越短。
实验例2:实施例7中光催化剂循环使用5次对反应底物结果的影响如表2所示:
Entry | Time(h) | Yield(%) | ee(%) |
1 | 24 | 55 | 84 |
2 | 24 | 53 | 80 |
3 | 24 | 58 | 83 |
4 | 24 | 56 | 86 |
5 | 24 | 53 | 87 |
由表2可知,本发明中手性醛化合物的产率为53%~58%,对映体过量百分数为80%~87%,说明手性醛化合物具有较高的对映体过量,催化性能好,结构稳定,能够使得反应选择性增加。
最后应说明的是:以上所述仅为本发明的优选实施例而已,并不用于限制本发明,尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (7)
1.一种苯并噁唑连接的共价有机框架不对称光催化制备手性醛化合物的方法,包括如下步骤:
以正辛醛和溴代丙二酸二乙酯为底物,苯并噁唑连接的共价有机框架为光催化剂,加入咪唑啉酮类的手性催化剂、溶剂以及2,6-二甲基吡啶,在氩气氛围中室温下可见光光照条件下搅拌反应,得到产物1,其化学式为:
所述手性催化剂为手性咪唑啉酮类催化剂,其化学式为:
所述苯并噁唑连接的共价有机框架为LZU-190;
所述苯并噁唑连接的共价有机框架LZU-190的制备方法为:
将前体1,3,5-三甲酰苯和2,5-二羟基-1,4-对苯二胺盐酸盐按摩尔比2:3混合,加入2,5-二羟基-1,4-对苯二胺盐酸盐摩尔用量的3倍苯并咪唑;加入组合溶剂N-甲基吡咯烷酮和均三甲苯,反应在185℃的密封的反应器中发生,反应时间为五天,即可获得苯并噁唑连接的共价有机框架LZU-190。
2.根据权利要求1所述的一种苯并噁唑连接的共价有机框架不对称光催化制备手性醛化合物的方法,其特征在于:所述的溶剂为乙腈,四氢呋喃,甲醇,N,N-二甲基甲酰胺,二氯甲烷或二甲基亚砜中的一种。
3.根据权利要求1所述的一种苯并噁唑连接的共价有机框架不对称光催化制备手性醛化合物的方法,其特征在于:所述苯并噁唑连接的共价有机框架LZU-190与底物的摩尔比为1:5-10。
4.根据权利要求1所述的一种苯并噁唑连接的共价有机框架不对称光催化制备手性醛化合物的方法,其特征在于:所述手性咪唑啉酮类催化剂与底物的摩尔比为1:3-10。
5.根据权利要求1所述的一种苯并噁唑连接的共价有机框架不对称光催化制备手性醛化合物的方法,其特征在于:通过离心分离LZU-190,用乙酸乙酯,丙酮,乙醇洗涤,收集清液,旋干,经柱层析得到目标产物。
6.根据权利要求5所述的一种苯并噁唑连接的共价有机框架不对称光催化制备手性醛化合物的方法,其特征在于:所述的柱层析是以石油醚和乙酸乙酯体积比5-50:1的混合溶剂为洗脱剂进行柱层析提纯。
7.根据权利要求1所述的一种苯并噁唑连接的共价有机框架不对称光催化制备手性醛化合物的方法,其特征在于:所得产物通过和手性醇化合物生成缩醛,然后用液体核磁氢谱检测或者直接用液相色谱仪检测。
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