CN113201108B - 一种(R)-CuTAPBP-COF聚合物及其制备方法及应用 - Google Patents
一种(R)-CuTAPBP-COF聚合物及其制备方法及应用 Download PDFInfo
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Abstract
本发明属于COF催化剂技术领域,具体涉及一种(R)‑CuTAPBP‑COF聚合物及其制备方法与应用。本发明提供的聚合物(R)‑CuTAPBP‑COF具有良好的光热转换性质,利用(R)‑CuTAPBP‑COF作为催化剂,通过光热转换可以有效地催化丙醛与4‑(溴甲基)吡啶反应得到血管生成抑制剂中间体(R)‑2‑甲基‑3‑(吡啶‑4‑基)丙醛,并且催化反应的产率和立体选择性都很高,实现了异相催化,同时可以重复利用五次以上,催化剂回收容易,提高了催化剂的利用率,降低了成本。
Description
技术领域
本发明属于COF催化剂技术领域,具体涉及一种(R)-CuTAPBP-COF聚合物及其制备方法与应用。
背景技术
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解,而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。
手性是自然界的基本特征。核酸、蛋白质和糖类等参与生命活动的重要生物分子大多都是手性的。近年来,人们对手性化合物如手性医药和手性农药的需求不断增长,极大地促进了不对称合成的发展。目前,不对称催化合成领域已经取得了巨大的进展,成千上万个手性配体分子和手性催化剂已经合成和报道,不对称催化合成已经应用到几乎所有的有机反应类型中,并开始成为工业上,尤其是制药工业合成手性物质的重要方法。
(R)-2-甲基-3-(吡啶-4-基)丙醛是一类重要的手性α-苄基醛化合物,可用于合成多种生物活性药物和天然产物,是血管生成抑制剂的关键中间体。该血管生成抑制剂能够有效地阻止或减缓肿瘤的生长和扩散,具有毒性低、不易产生耐药性的特点,现已普遍用于恶性肿瘤、糖尿病性视网膜病变和年龄相关性黄斑变性等多种疾病的治疗。
目前,均相催化是不对称催化合成(R)-2-甲基-3-(吡啶-4-基)丙醛的主流,但是均相催化剂存在不易分离和难以回收再利用等问题,相比之下,异相手性催化剂具有可重复利用的优点,符合可持续发展的要求,展现出广阔的发展前景,因此,提供一种有效的催化合成(R)-2-甲基-3-(吡啶-4-基)丙醛的异相手性催化剂具有重要的意义。
发明内容
为了解决现有技术的不足,本发明提供一种二维手性(R)-CuTAPBP-COF型催化剂,该聚合物能够用于催化合成血管生成抑制剂中间体,具有良好的催化效率,并且能多次重复使用,具有广阔的应用前景。
为了实现上述目的,本发明第一方面提供一种聚合物(R)-CuTAPBP-COF,所述聚合物的结构如下式1所示:
本发明第二方面,提供聚合物(R)-CuTAPBP-COF作为催化剂的应用。
优选的,所述催化剂为血管生成抑制剂中间体的催化剂;更进一步的,为催化丙醛与4-(溴甲基)吡啶反应得到血管生成抑制剂中间体(R)-2-甲基-3-(吡啶-4-基)丙醛的催化剂。
本发明第三方面提供一种聚合物(R)-CuTAPBP-COF的制备方法,所述制备方法以Cu-TAPP和(R)-BIONLPA-DA为反应原料;其中,Cu-TAPP的结构如下式2所示,(R)-BIONLPA-DA的结构如下式3所示:
本发明的一个或多个实施方式至少具有以下有益效果:
(1)本发明提供的聚合物(R)-CuTAPBP-COF具有良好的光热转换性质,利用(R)-CuTAPBP-COF作为催化剂,通过光热转换可以有效地催化丙醛与4-(溴甲基)吡啶反应得到血管生成抑制剂中间体(R)-2-甲基-3-(吡啶-4-基)丙醛,并且催化反应的产率和立体选择性都很高,实现了异相催化,同时可以重复利用五次以上,催化剂回收容易,提高了催化剂的利用率,降低了成本。
(2)本发明以聚合物(R)-CuTAPBP-COF作为血管生成抑制剂中间体的催化剂,价格低廉、产率和纯度高,易于分离,避免了合成路线中的拆分与消旋,实验过程中无特殊、有毒有害试剂使用,反应条件温和,符合节能和环保的要求。
附图说明
构成本发明的一部分的说明书附图用来提供对本发明的进一步理解,本发明的示意性实施例及其说明用于解释本发明,并不构成对本发明的不当限定。
图1为实施例2制备的(R)-CuTAPBP-COF的扫描电镜图;
图2是实施例2制备的(R)-CuTAPBP-COF的热重图;
图3是实施例2制备的(R)-CuTAPBP-COF的PXRD图;
图4是实施例2制备的(R)-CuTAPBP-COF的固体核磁谱图;
图5是实施例2制备的(R)-CuTAPBP-COF的N2吸附图;
图6是实施例2制备的(R)-CuTAPBP-COF的紫外吸收谱图;
图7是实施例2制备的(R)-CuTAPBP-COF的光热转换升温图;
图8是实施例2制备的(R)-CuTAPBP-COF催化5次后的PXRD图;
图9是实施例2制备的(R)-CuTAPBP-COF催化后的气相图;
图10是实施例2制备的(R)-CuTAPBP-COF催化的液相图;
图11是实施例2制备的(R)-CuTAPBP-COF催化的质谱图;
图12是实施例2制备的(R)-CuTAPBP-COF催化的核磁图。
具体实施方式
应该指出,以下详细说明都是示例性的,旨在对本发明提供进一步的说明。除非另有指明,本文使用的所有技术和科学术语具有与本发明所属技术领域的普通技术人员通常理解的相同含义。
需要注意的是,这里所使用的术语仅是为了描述具体实施方式,而非意图限制根据本发明的示例性实施方式。如在这里所使用的,除非上下文另外明确指出,否则单数形式也意图包括复数形式,此外,还应当理解的是,当在本说明书中使用术语“包含”和/或“包括”时,其指明存在特征、步骤、操作、器件、组件和/或它们的组合。
正如背景技术所介绍的,现有技术中均相催化剂催化合成(R)-2-甲基-3-(吡啶-4-基)丙醛存在不易分离和回收困难等问题,为了解决该技术问题,本发明第一方面提供一种聚合物(R)-CuTAPBP-COF,所述聚合物的结构如下式1所示:
优选的,聚合物为C2的手性空间群。
本发明通过Materials Studio(ver.8.0)软件对(R)-CuTAPBP-COF的结构进行了模拟,结果表明,(R)-CuTAPBP-COF结晶于手性空间群C2,采取AB交错堆积方式,Pawley精修后的晶胞参数为α=γ=90°,β=104.46°,精修系数Rwp和Rp值分别为2.04%和2.01%,其晶胞参数和原子坐标见表1。
表1(R)-CuTAPBP-COF的晶胞参数和原子坐标
本发明第二方面,提供聚合物(R)-CuTAPBP-COF作为催化剂的应用。
进一步的,所述催化剂为血管生成抑制剂中间体的催化剂;更进一步的,为催化丙醛与4-(溴甲基)吡啶反应得到血管生成抑制剂中间体(R)-2-甲基-3-(吡啶-4-基)丙醛的催化剂。
优选的,所述血管生成抑制剂中间体的制备通过丙醛与4-(溴甲基)吡啶在可见光照射条件下反应。
所述血管生成抑制剂中间体的反应方程式如下:
经本发明研究表明,该聚合物作为催化丙醛与4-(溴甲基)吡啶反应生成血管生成抑制剂中间体(R)-2-甲基-3-(吡啶-4-基)丙醛的催化剂,五次催化循环后,框架结构没有改变,并且多次重复使用后,产率没有发生明显的降低,具有良好的稳定性和催化效率。
本发明第三方面提供一种聚合物(R)-CuTAPBP-COF的制备方法,所述制备方法以Cu-TAPP和(R)-BIONLPA-DA为反应原料;其中,Cu-TAPP的结构如下式2所示,(R)-BIONLPA-DA的结构如下式3所示:
进一步的,所述制备方法包括:将Cu-TAPP和(R)-BIONLPA-DA加入乙醇、均三甲苯和稀醋酸的混合溶液中进行反应,即所述聚合物(R)-CuTAPBP-COF。
优选的,所述反应温度为110-120℃。
优选的,所述反应时间为3-3.5d。
优选的,所述Cu-TAPP和(R)-BIONLPA-DA的摩尔质量比为1:2。
优选的,所述乙醇、均三甲苯和稀醋酸的体积比为17:3:2。
进一步优选的,所述制备方法还包括:反应结束后,收集固体部分采用乙醇洗涤后得到紫黑色粉末,即所述聚合物(R)-CuTAPBP-COF。
在本发明的一个或多个实施方式中,所述(R)-BIONLPA-DA的合成方法为:
氮气下,称取适量(R)-BIONLDH-DA,加入无水吡啶,然后向反应体系中滴加POCl3,混合反应,得到(R)-BIONLPA-DA。
进一步的,(R)-BIONLDH-DA、POCl3和无水吡啶的质量体积比为0.56mg:457μL:20mL;
进一步的,滴加POCl3的过程在0℃下进行;
进一步的,加入无水吡啶后先在100-105℃下回流12-14h,然后降温至0℃,滴加POCl3,加热至100-105℃继续反应45-48h,再将反应体系冷却至0℃,加入水在100℃下加热回流48h。
反应结束后恢复至室温,向反应体系中加入盐酸酸化,分液取有机相,用二氯甲烷萃取三次,合并有机层后旋蒸得到黄色固体,将粗产品进行柱层析(洗脱剂为乙酸乙酯:石油醚=1:1),旋蒸并真空干燥后得到浅黄色产物(R)-BIONLPA-DA。
在本发明的一个或多个实施方式中,所述(R)-BIONLDH-DA的制备方法为:
取适量三溴化硼,加入二氯甲烷在室温下搅拌,缓慢滴加(R)-BIONLDE-DA的二氯甲烷溶液,反应得到黄色固体(R)-BIONLDH-DA。
其中,
进一步的,三溴化硼、二氯甲烷、(R)-BIONLDE-DA的添加比为570μL:10mL:0.62mg;
更进一步的,所述反应过程为:在室温下反应22-24h,反应结束后冷却至0℃,滴加水猝灭反应,继续搅拌1-1.5h,最后向反应体系中加入二氯甲烷,分液取有机相,水相用乙酸乙酯萃取三次,合并有机层后旋蒸并真空干燥。
在本发明的一个或多个实施方式中,所述(R)-BIONLDE-DA的制备方法为:
氮气下,称取(R)-DCDB、4-甲酰基苯硼酸、无水K2CO3、Pd[P(Ph)3]4置于两口烧瓶中,加入四氢呋喃/水(3:1)进行反应,反应结束后分液取上层有机层,水层用二氯甲烷萃取,合并有机层后旋蒸得到橙色固体的粗产品。
进一步的,(R)-DCDB、4-甲酰基苯硼酸、无水K2CO3、Pd[P(Ph)3]4的摩尔比为1:2:6:0.06;
进一步的,混合溶剂在80℃下加热回流36h;
更进一步的,将粗产品进行柱层析(洗脱剂为二氯甲烷:石油醚=1:1),旋蒸并真空干燥后得到浅黄色固体(R)-BIONLDE-DA。
在本发明的一个或多个实施方式中,所述(R)-DCDB的制备方法为:
称取(R)-DCDE置于100mL三口烧瓶中,依次加入二氯甲烷、液溴,然后加入Na2S2O3的水溶液淬灭反应,分液取有机相,旋蒸并真空干燥得到黄色固体(R)-DCDB;
进一步的,(R)-DCDE、液溴、Na2S2O3的摩尔比为1:24:7.4;
进一步的,加入二氯甲烷后,冷却至0℃,搅拌条件下缓慢滴加液溴;
进一步的,加入液溴后在0℃下反应24h后,再加入Na2S2O3;
进一步的,分液取有机相后,用饱和NaCl溶液洗涤三次,合并有机相进行旋蒸。
在本发明的一个或多个实施方式中,所述(R)-DCDE的制备方法为:
N2保护下,将(R)-DBDE、氯化亚铜置于100mL三口烧瓶中,加入DMF进行反应,反应结束后趁热过滤,将滤液倒入水中,再次过滤得到浅黄色固体;将粗产品进行柱层析(洗脱剂为二氯甲烷),旋蒸并真空干燥后得到黄色固体(R)-DCDE。
优选的,(R)-DBDE、氯化亚铜、DMF的添加比为4.97g:2.20g:15mL;
优选的,在110-120℃下回流45-48h进行反应;
在本发明的一个或多个实施方式中,所述(R)-DBDE的制备方法为:
称取(R)-DB、无水K2CO3、溴乙烷置于两口烧瓶中,加入丙酮,加热回流,反应结束后冷却至室温,过滤取滤液,旋蒸并真空干燥后得到黄色固体(R)-DBDE。
其中,(R)-DB、无水K2CO3、溴乙烷的摩尔比为1:4:6;
进一步的,加热回流时间为48h。
在本发明的一个或多个实施方式中,所述(R)-DB的制备方法为:
称取(R)-1,1'-联-2-萘酚置于100mL三口烧瓶中,依次加入二氯甲烷、液溴,反应结束后,反应液由橙色变为浅黄色,过滤反应液,合并有机相后旋蒸并真空干燥,得到浅黄色固体(R)-DB。
进一步的,所述步骤(1)中,(R)-1,1'-联-2-萘酚、液溴、Na2S2O3的摩尔比为10:25.2:7.4;
进一步的,加入二氯甲烷,冷却至0℃,搅拌条件下缓慢滴加液溴,在0℃下反应24h后,加入Na2S2O3的水溶液淬灭反应,并继续搅拌2h。
为了使得本领域技术人员能够更加清楚地了解本发明的技术方案,以下将结合具体的实施例详细说明本发明的技术方案。
实施例1:(R)-BIONLPA-DA的合成
称取(R)-1,1'-联-2-萘酚(10.0mmol,2.86g)置于100mL三口烧瓶中,加入二氯甲烷(20mL),冷却至0℃,搅拌条件下缓慢滴加液溴(25.2mmol,4.00g),在0℃下反应24h后,加入Na2S2O3(7.4mmol,1.20g)的水溶液淬灭反应,继续搅拌2h。反应结束后,反应液由橙色变为浅黄色。过滤反应液,将滤液转移到分液漏斗中,有机相用饱和NaCl溶液洗涤三次,合并有机相后旋蒸并真空干燥,得到浅黄色固体(R)-DB。
称取(R)-DB(10.0mmol,4.44g)、无水K2CO3(40.0mmol,5.50g)、溴乙烷(60.0mmol,7.00g)置于100mL两口烧瓶中,加入丙酮(40mL),加热回流48h。反应结束后冷却至室温,过滤取滤液,旋蒸并真空干燥后得到黄色固体(R)-DBDE。
N2保护下,将(R)-DBDE(10.0mmol,4.97g)、氯化亚铜(22.0mmol,2.20g)置于100mL三口烧瓶中,加入DMF(15mL),在110℃下回流48h。反应结束后趁热过滤,将滤液倒入水(300mL)中,再次过滤得到浅黄色固体。将粗产品进行柱层析(洗脱剂为二氯甲烷),旋蒸并真空干燥后得到黄色固体(R)-DCDE。
称取(R)-DCDE(1.0mmol,0.41g)置于100mL三口烧瓶中,加入二氯甲烷(30mL),冷却至0℃,搅拌条件下缓慢滴加液溴(24.0mmol,1.25mL),在0℃下反应24h后,加入Na2S2O3(7.4mmol,1.20g)的水溶液淬灭反应,继续搅拌2h。分液取有机相,用饱和NaCl溶液洗涤三次,合并有机相,旋蒸并真空干燥得到黄色固体(R)-DCDB。
氮气下,称取(R)-DCDB(1.0mmol,0.57g)、4-甲酰基苯硼酸(2.0mmol,0.36g)、无水K2CO3(6.0mmol,0.82g)、Pd[P(Ph)3]4(0.06mmol,0.08g)置于100mL两口烧瓶中,加入四氢呋喃/水(3:1,40mL)混合溶剂在80℃下加热回流36h。反应结束后趁热分液,取上层有机层,水层用二氯甲烷(20mL)萃取三次,合并有机层后旋蒸得到橙色固体。将粗产品进行柱层析(洗脱剂为二氯甲烷:石油醚=1:1),旋蒸并真空干燥后得到浅黄色固体(R)-BIONLDE-DA。
量取三溴化硼(6.0mmol,570μL)置于50mL两口烧瓶中,加入二氯甲烷(10mL)在室温下搅拌,缓慢滴加(R)-BIONLDE-DA(1.0mmol,0.62mg)的二氯甲烷(10mL)溶液,在室温下反应24h。反应结束后冷却至0℃,滴加水猝灭反应,继续搅拌1h。向反应体系中加入二氯甲烷(20mL),分液取有机相,水相用乙酸乙酯萃取三次,合并有机层后旋蒸并真空干燥,得到黄色固体(R)-BIONLDH-DA。
氮气下,称取(R)-BIONLDH-DA(1.0mmol,0.56mg)置于50mL两口烧瓶中,加入无水吡啶(20mL)在100℃下回流12h。然后降温至0℃,向反应体系中滴加POCl3(4.9mmol,457μL),加热至100℃继续反应48h。再将反应体系冷却至0℃,加入水(4.5mL)在100℃下加热回流48h。反应结束后恢复至室温,向反应体系中加入盐酸酸化。分液取有机相,用二氯甲烷萃取三次,合并有机层后旋蒸得到黄色固体。将粗产品进行柱层析(洗脱剂为乙酸乙酯:石油醚=1:1),旋蒸并真空干燥后得到浅黄色产物(R)-BIONLPA-DA。
实施例2:(R)-CuTAPBP-COF的合成
称取Cu-TAPP(0.05mmol,36.60mg)、(R)-BIONLPA-DA(0.1mmol,61.60mg)置于10mL耐压管中,加入乙酸(9M,0.2mL)、乙醇/均三甲苯(5:1,2mL)混合溶剂,超声10min使混合均匀。用液氮冷冻脱气三次,在120℃下加热72h,反应结束后冷却至室温,静置48h。离心收集固体,用乙醇反复洗涤,真空干燥后得到紫黑色产物(R)-CuTAPBP-COF。
本实施例通过扫描电镜、热重、PXRD、固体核磁、N2吸附表征了该化合物,结果分别见图1、2、3、4和5,由图1和图5可以证实所述聚合物具有孔结构,催化剂(R)-CuTAPBP-COF的热重(图2),PXRD(图3)、固体核磁(图4)说明该COF为具有高热稳定性的晶态多孔材料。
由上述方法制备得到的(R)-CuTAPBP-COF在甲醇溶液中的紫外吸收谱图见图6,从该图中可以看出,其在420nm处有最大吸收,因此测试了在420nm的光照下该COF的光热转换升温(图7),可见,随着辐照时间的延长,具有显著的升温效果,当辐照时间到960s时,温度达到最高,继续延长辐照时间,升温效果降低。
实施例3:(R)-CuTAPBP-COF催化血管生成抑制剂中间体的反应。
本实施例中反应方程式如下:
将催化剂(R)-CuTAPBP-COF(10.0mg,1.8mol%Cu,1.7mol%P)、丙醛(0.5mmol,79μL)、4-(溴甲基)吡啶(0.25mmol,43mg)、2,6-二甲基吡啶(0.75mmol,88μL)置于石英管中,加入甲醇(1.5mL),用氙灯(λ=420nm,强度为2.5W cm-2)照射,在室温下搅拌5h,得到(R)-2-甲基-3-(吡啶-4-基)丙醛产物。催化反应产率由GC分析测定,产物ee值由HPLC分析测定,其结果分别见图9(气相图)、图10(液相图)、图11(质谱图)、图12(核磁图),图9-12证明了(R)-2-甲基-3-(吡啶-4-基)丙醛产物的生成。
实验例4:(R)-CuTAPBP-COF催化血管生成抑制剂中间体的反应的循环次数。
通过气相色谱追踪反应,反应结束后,离心回收催化剂,直接投入下一循环反应,按照上述条件,催化剂使用5个循环,反应液通过气相色谱(丙醛为内标)计算产率,反应产物的ee值由液相色谱分析测定,催化效果如表2所示,从表2可以看出,催化剂进行两次循环后,产物的产率和ee值基本保持一致,五次循环后,仅表现出略微的降低趋势,体现出该催化剂优异的稳定性,可以重复利用五次以上,能显著提高催化剂的利用率,并降低生产成本。
五次循环反应完成后将溶液离心后,得到的催化剂用乙醇洗涤三次,90℃真空干燥后通过PXRD表征,如图8所示,可以看出(R)-CuTAPBP-COF仍保持原来的框架,进一步证实了该催化剂的稳定性,能够在多次循环催化后维持原来的结构框架。
表2(R)-CuTAPBP-COF催化反应5个循环的产率和立体选择性
a:产率通过气相色谱测定b:ee值由液相色谱分析测定
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,对于本领域的技术人员来说,本发明可以有各种更改和变化。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 (13)
2.权利要求1所述的聚合物(R)-CuTAPBP-COF,其特征在于:所述聚合物为C2的手性空间群。
3.权利要求1所述的聚合物(R)-CuTAPBP-COF作为催化剂的应用。
4.权利要求3所述的聚合物(R)-CuTAPBP-COF的应用,其特征在于:所述催化剂为血管生成抑制剂中间体的催化剂。
5.权利要求4所述的聚合物(R)-CuTAPBP-COF的应用,其特征在于:作为催化丙醛与4-(溴甲基)吡啶反应得到血管生成抑制剂中间体(R)-2-甲基-3-(吡啶-4-基)丙醛的催化剂。
7.如权利要求6所述的制备方法,其特征在于:将Cu-TAPP和(R)-BIONLPA-DA加入乙醇、均三甲苯和稀醋酸的混合溶液中进行反应,即所述聚合物(R)-CuTAPBP-COF。
8.如权利要求7所述的制备方法,其特征在于:所述反应温度为110-120℃。
9.如权利要求7所述的制备方法,其特征在于:所述反应时间为3-3.5d。
10.如权利要求7所述的制备方法,其特征在于:所述Cu-TAPP和(R)-BIONLPA-DA的摩尔质量比为1∶2。
11.如权利要求7所述的制备方法,其特征在于:所述乙醇、均三甲苯和稀醋酸的体积比为17∶3∶2。
12.如权利要求7所述的制备方法,其特征在于:所述制备方法还包括:反应结束后,收集固体部分采用乙醇洗涤后得到紫黑色粉末,即所述聚合物(R)-CuTAPBP-COF。
13.如权利要求7所述的制备方法,其特征在于:所述(R)-BIONLPA-DA的合成方法为:
称取(R)-1,1′-联-2-萘酚置于100mL三口烧瓶中,依次加入二氯甲烷、液溴,加入二氯甲烷,冷却至0℃,搅拌条件下缓慢滴加液溴,在0℃下反应24h后,加入Na2S2O3的水溶液淬灭反应,并继续搅拌2h;(R)-1,1′-联-2-萘酚、液溴、Na2S2O3的摩尔比为10∶25.2∶7.4;反应结束后,反应液由橙色变为浅黄色,过滤反应液,合并有机相后旋蒸并真空干燥,得到浅黄色固体(R)-DB;
称取(R)-DB、无水K2CO3、溴乙烷置于两口烧瓶中,(R)-DB、无水K2CO3、溴乙烷的摩尔比为1∶4∶6;加入丙酮,加热回流,加热回流时间为48h;反应结束后冷却至室温,过滤取滤液,旋蒸并真空干燥后得到黄色固体(R)-DBDE;
N2保护下,将(R)-DBDE、氯化亚铜置于100mL三口烧瓶中,加入DMF进行反应,(R)-DBDE、氯化亚铜、DMF的添加比为4.97g∶2.20g∶15mL,在110-120℃下回流45-48h进行反应,反应结束后趁热过滤,将滤液倒入水中,再次过滤得到浅黄色固体;以二氯甲烷为洗脱剂,将粗产品进行柱层析,旋蒸并真空干燥后得到黄色固体(R)-DCDE;
称取(R)-DCDE置于100mL三口烧瓶中,,加入二氯甲烷后,冷却至0℃,搅拌条件下缓慢滴加液溴;其中加入液溴后在0℃下反应24h后,加入Na2S2O3的水溶液淬灭反应;其中(R)-DCDE、液溴、Na2S2O3的摩尔比为1∶24∶7.4;分液取有机相,用饱和NaCl溶液洗涤三次,合并有机相进行旋蒸并真空干燥得到黄色固体(R)-DCDB;
氮气下,称取(R)-DCDB、4-甲酰基苯硼酸、无水K2CO3、Pd[P(Ph)3]4置于两口烧瓶中,(R)-DCDB、4-甲酰基苯硼酸、无水K2CO3、Pd[P(Ph)3]4的摩尔比为1∶2∶6∶0.06;加入四氢呋喃/水混合液进行反应,反应结束后分液取上层有机层,水层用二氯甲烷萃取,合并有机层后旋蒸得到橙色固体的粗产品;洗脱剂为二氯甲烷∶石油醚=1∶1,将粗产品进行柱层析,旋蒸并真空干燥后得到浅黄色固体(R)-BIONLDE-DA;
取适量三溴化硼,加入二氯甲烷在室温下搅拌反应22-24h,缓慢滴加(R)-BIONLDE-DA的二氯甲烷溶液,其中,三溴化硼、二氯甲烷、(R)-BIONLDE-DA的添加比为570μL∶10mL∶0.62mg,反应结束后冷却至0℃,滴加水猝灭反应,继续搅拌1-1.5h,最后向反应体系中加入二氯甲烷,分液取有机相,水相用乙酸乙酯萃取三次,合并有机层后旋蒸并真空干燥,得到黄色固体(R)-BIONLDH-DA;
氮气下,称取适量(R)-BIONLDH-DA,加入无水吡啶,加入无水吡啶后先在100-105℃下回流12-14h,然后降温至0℃,滴加POCl3,加热至100-105℃继续反应45-48h,再将反应体系冷却至0℃,加入水在100℃下加热回流48h;其中(R)-BIONLDH-DA、POCl3和无水吡啶的质量体积比为0.56mg∶457μL∶20mL;反应结束后恢复至室温,向反应体系中加入盐酸酸化,分液取有机相,用二氯甲烷萃取三次,合并有机层后旋蒸得到黄色固体,将粗产品进行柱层析,旋蒸并真空干燥后得到浅黄色产物(R)-BIONLPA-DA。
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