CN111763224B - 一种基于硒导向碳氢键硼化快速制备苄基硒类化合物的方法 - Google Patents
一种基于硒导向碳氢键硼化快速制备苄基硒类化合物的方法 Download PDFInfo
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- NSXOOKQXYVJEAP-UHFFFAOYSA-N phenylmethaneselenol Chemical compound [SeH]CC1=CC=CC=C1 NSXOOKQXYVJEAP-UHFFFAOYSA-N 0.000 title claims abstract description 13
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
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Abstract
本发明提供了一种基于硒导向碳氢键硼化快速制备苄基硒类化合物的方法,属于有机合成领域。本发明在较为温和的条件下,以含硒有机化合物(苄基苯基硒衍生物)为原料,以廉价的频那醇硼烷为硼源,以双联硼频哪醇酸酯作添加剂,以过渡金属铱为催化剂,催化在邻位进行的碳氢键活化的反应,从而制备出有机硒化合物的一系列硼化的产物。本发明的优点是:产物的收率较高,反应条件温,且有机硒硼化物能方便快捷转换为新的有机硒化合物并且保持空间构型不变,保持良好的活性为有机硒的合成提供了新的方法。因此,本发明为今后包含此结构的其他高价值化合物的工业化生产提供了一种有效的方案。
Description
技术领域
本发明属于有机化学包括医药中间体制备及相关化学技术领域,具体涉及一种基于硒导向碳氢键硼化快速制备苄基硒类化合物的方法。
背景技术
含硒的有机硼中间体在有机合成中是一类非常有用的中间体,可以转化为其他化合物并保持其空间构型不变。因此可以合成含硒的有机硼中间体,来拓展硒化合物的种类。有机硒化合物在医药、保健、工业等方面有着广泛的应用,在生命科学、信息科学等领域也有着潜在的应用价值[刘秀然,唐关平,邱肇炉,许想姣.硒及其化合物的发展现状[J].广州化工,2017,45(22):14-16.王晓民.硒及其化合物的生产、消费和应用前景[J].世界有色金属,2011(01):28-31.Gandin V,Khalkar P,Braude J,et al.Organic seleniumcompounds as potential chemotherapeutic agents for improved cancer treatment[J].Free Radical Biology and Medicine,2018,127.]。因此这类化合物的制备在工业的应用中是非常重要的一个步骤。
目前有机硒化合物的合成方法主要有生物合成法、化学合成法两大类,以化学合成法为主。但目前已有的化学合成法比较少,能合成的含硒化合物种类较少,并且这些方法或多或少都存在原料不易获得且价格较高,没有生产效益,或者原料有剧毒,对人体和环境伤害大等一系列问题。[金小红.有机硒类化合物的合成及其生物活性[J].国外医药(抗生素分册),2018,39(06):104-110.谭龙飞,郭宝江.合成有机硒化合物的研究进展[J].食品与机械,1998(3):14-14].因此寻找到一种原料便宜、方法便捷、环保的方法来合成便捷合成多种类含硒化合物的方法就成了当务之急。近年来,在过渡金属配合物存在下,以含氧或硫基团作为导向基,进行了一系列邻位碳氢键硼化反应取得了重大的进展[Hong LiangLi,Yoichiro Kuninobu,Motomu Kanai.Lewis Acid-Base Interaction-Controlledortho-Selective C-H Borylation of Aryl Sulfides[J].Angew.Chem.2017(129)1517–1521.Miura W,Hirano K,Miura M.Rhodium-Catalyzed C6-Selective C-H Borylationof 2-Pyridones[J].Organic Letters,2016:acs.orglett.6b01762.Li Liu,GuanghuiWang,Jiao Jiao,and Pengfei Li,Sulfur-Directed Ligand-Free C-H Borylation byIridium Catalysis[J].Organic Letters 2017 19(22),6132-6135.Gam J,Djb L,W O,et al.Synthesis of Selenium-Quinone Hybrid Compounds withPotential Antitumor Activity via Rh-Catalyzed C-H Bond Activation and ClickReactions[J].Molecules,2017,23(1):83.]。
发明内容
本发明的目的是提供一种基于硒导向碳氢键硼化快速制备苄基硒类化合物的方法。以硒作为导向基,用频那醇硼烷作为硼源,获得有机硒硼化合物。本发明具有硼源廉价易得,反应条件较为温和,收率较高,重现性好,应用范围较广。
本发明提供了一种基于硒导向碳氢键硼化快速制备苄基硒类化合物的方法,以铱金属作为反应的催化剂,硒作为导向基,用频那醇硼烷作为硼源,获得有机硒硼化合物。
具体步骤为:
将铱催化剂和配体加入史莱克管中,在惰性气体保护下,加入溶剂,在一定温度下搅拌20min;将装有催化剂和配体络合物的史莱克管中加入硼源,底物,添加剂;反应过程中用TLC进行跟踪以决定具体的反应时间;合成路线为:
反应结束后,将有机溶剂旋干,用柱层析进行纯化得到有机硒硼化产物,洗脱剂为石油醚和乙酸乙酯的混合溶液。
所述铱催化剂为(1,5-环辛二烯)二氯化铱(I)二聚体;
所述配体为三苯基膦,三环己基膦,3-(五氟)环己基膦或者三丁基膦;
所述硼源为频那醇硼烷;
所述添加剂为双联硼频哪醇酸酯;
R1选自氢、卤素、烷基;
R2选自烷基、芳基;
R1和R2相同或不同。
其中:反应温度为20-200℃,反应时间为0.5h~48h;
其中:含硒化合物为苄基苯基硒及衍生物。
其中:含硒化合物在溶剂中的摩尔浓度为0.01~10mmol/mL。
其中:反应溶剂为四氢呋喃、二氯甲烷、二氯乙烷、甲苯、1,4-二氧六环、乙腈、乙酸乙酯、苯、正己烷中的一种或一种以上混合。
其中:配体用量为2%~100%。
其中:催化剂的用量为1%~50%。
其中;硼源用量为0.5~25当量。
其中:添加剂用量为0.5~10当量。
处理及纯化方法:先将反应后的溶剂旋干,进一步用柱层析法纯化分离;柱层析可以选择200~300目的硅胶或碱性氧化铝作为固定相,洗脱剂一般选择石油醚和乙酸乙酯的混合体系。
发明具有以下优点:
1、产率较高,反应条件相对温和。
2、硼源廉价易得,环保安全,重现性好。
3、与传统方法相比较,该为合成有机硒化合物提供一种更方便快捷的方法。
附图说明
图1为实施例1制备的2-(3-氟-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷的核磁共振氢谱和核磁共振碳谱;
图2为实施例2制备的2-(3-氯-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷;
图3为实施例3制备的2-(3-溴-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷;
图4为实施例4制备的4,4,5,5-四甲基-2-(3-三氟甲基-2-((苯硒基)甲基)苯基)-1,3,2-二氧杂硼烷;
图5为实施例5制备的4,4,5,5-四甲基-2-(3-甲基-2-((苯硒基)甲基)苯基)-1,3,2-二氧杂硼烷;
图6为实施例6制备的4,4,5,5-四甲基-2-(2-(((苯硒基)甲基)-4-(三氟甲基)苯基)-1,3,2-二氧杂硼烷;
图7为实施例7制备的2-(4-溴-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷;
图8为实施例8制备的2-(3,4-二氟-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷;
图9为实施例9制备的2-(2-((((4-氟苯基)硒代)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷;
图10为实施例10制备的4,4,5,5-四甲基-2-(2-(((苯硒基)甲基)-4-(甲基)苯基)-1,3,2-二氧杂硼烷;
图11为实施例11制备的4,4,5,5-四甲基-2-(2-((苯硒基)甲基)苯基)-1,3,2-二氧杂硼烷的核磁共振氢谱和核磁共振碳谱;
图12为实施例12制备的2,2'-(5-氟-2-((苯硒基)甲基)-1,3-亚苯基)双(4,4,5,5-四甲基-1,3,2-二氧杂硼烷)的核磁共振氢谱和核磁共振碳谱;
具体实施方式
本发明所运用的方法,制备出的有机硒硼化合物收率较高,反应环境要求低,条件相对温和,原料普遍适用性好,硼源廉价易得,扩大量反应仍然能表现出好的重现性。因此,本发明为今后包含此结构的其他高价值化合物的工业化生产提供了一种有效的方案。
本发明在较为温和的条件下,以含硒有机化合物(苄基苯基硒衍生物)为原料,以廉价的频那醇硼烷为硼源,以过渡金属铱为催化剂,催化在邻位进行的碳氢键活化的反应,从而制备出有机硒化合物的一系列硼化的产物。本发明的优点是:产物的收率较高,反应条件温,且有机硒硼化物能方便快捷转换为新的有机硒化合物并且保持空间构型不变,保持良好的活性为有机硒的合成提供了新的方法。因此,本发明为今后包含此结构的其他高价值化合物的工业化生产提供了一种有效的方案。
下面结合具体实施方式对本发明的技术方案进一步的说明和描述,但并不因此而限制本发明。在本领域内的技术人员对本发明所做的简单替换或改进均属于本发明所保护的技术方案之内。
实施例1
合成2-(3-氟-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷。
称取(1,5-环辛二烯)二氯化铱(I)二聚体(2.7mg,0.004mmol)三环己基膦(2.2mg,0.008mmol)加入史莱克管中,在惰性气体保护下,在80℃反应20min,加入双联硼酸频那醇酯(25.4mg,0.1mmol),加(2-氟苄基)(苯基)硒(53.2mg,0.2mmol)和频哪醇硼烷(100μL,6.8mmol)80℃搅拌反应24h。所得反应物用硅胶柱(石油醚/乙酸乙酯)纯化得到2-(3-氟-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷(62mg)产率80%。
2-(3-氟-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷的结构式如下:
产物2-(3-氟-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷的核磁共振氢谱和核磁共振碳谱如图1所示:1H NMR(600MHz,CDCl3)δ7.51-7.45(m,1H),7.42-7.35(m,2H),7.18-7.09(m,3H),7.09-7.05(m,1H),6.96-6.91(m,1H),4.44(s,2H),1.24(s,12H).13C NMR(151MHz,CDCl3)δ160.8(d,J=247.6Hz),134.2,132.8(d,J=12.1Hz),131.9(d,J=4.5Hz),130.7,128.8,127.7(d,J=7.5Hz),127.3,119.0(d,J=22.6Hz),84.0,25.0,23.7(d,J=4.5Hz).HRMS(ESI):Calculated for C19H22BFO2Se[M+Na]+:415.0754,Found:415.0755.
实施例2
合成2-(3-氯-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷。
称取(1,5-环辛二烯)二氯化铱(I)二聚体(2.7mg,0.004mmol)三环己基膦(2.2mg,0.008mmol)加入史莱克管中,在惰性气体保护下,在80℃反应20min,加入双联硼酸频那醇酯(25.4mg,0.1mmol),加入(2-氯苄基)(苯基)硒(56.4mg,0.2mmol)和频哪醇硼烷(100μL,6.8mmol)80℃搅拌反应24h。所得反应物用硅胶柱(石油醚/乙酸乙酯)纯化得到2-(3-氯-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷(62mg)产率76%。
2-(3-氯-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷的结构式如下:
2-(3-氯-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷的核磁共振氢谱和核磁共振碳谱如图2所示:1H NMR(600MHz,CDCl3)δ7.70-7.47(m,1H),7.42-7.37(m,2H),7.33-7.27(m,1H),7.20-7.10(m,3H),7.08-7.03(m,1H),4.62(s,2H),1.21(s,12H).13C NMR(151MHz,CDCl3)δ142.9,134.8,134.4,132.2,130.8,128.8,127.4,127.4,84.1,28.7,24.9.HRMS(ESI):Calculated for C19H22BClO2Se[M+Na]+:431.0459,Found:431.0462.
实施例3
合成2-(3-溴-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷。
称取(1,5-环辛二烯)二氯化铱(I)二聚体(2.7mg,0.004mmol)三环己基膦(2.2mg,0.008mmol)加入史莱克管中,在惰性气体保护下,在80℃反应20min,加入双联硼酸频那醇酯(25.4mg,0.1mmol),加入(2-溴苄基)(苯基)硒(65.2mg,0.2mmol)和频哪醇硼烷(100μL,6.8mmol)80℃搅拌反应24h。所得反应物用硅胶柱(石油醚/乙酸乙酯)纯化得到2-(3-溴-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷(59mg)产率66%。
2-(3-溴-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷的结构式如下:
2-(3-溴-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷的核磁共振氢谱和核磁共振碳谱如图3所示:1H NMR(600MHz,CDCl3)δ7.74-7.68(m,1H),7.60-7.54(m,1H),7.50-7.45(m,2H),7.28-7.18(m,3H),7.08-6.98(m,1H),4.73(s,2H),1.27(s,12H).13C NMR(151MHz,CDCl3)δ144.5,135.7,135.5,134.4,130.8,128.8,127.7,127.4,125.9,84.2,31.7,24.9.HRMS(ESI):Calculated for C19H22BBrO2Se[M+Na]+:474.9954,Found:474.9953.
实施例4
合成4,4,5,5-四甲基-2-(3-三氟甲基-2-((苯硒基)甲基)苯基)-1,3,2-二氧杂硼烷。
称取(1,5-环辛二烯)二氯化铱(I)二聚体(2.7mg,0.004mmol)三环己基膦(2.2mg,0.008mmol)加入史莱克管中,在惰性气体保护下,在80℃反应20min,加入双联硼酸频那醇酯(25.4mg,0.1mmol),加入(2-三氟甲基苄基)(苯基)硒(63.2mg,0.2mmol)和频哪醇硼烷(100μL,6.8mmol)80℃搅拌反应24h。所得反应物用硅胶柱(石油醚/乙酸乙酯)纯化得到4,4,5,5-四甲基-2-(3-三氟甲基-2-((苯硒基)甲基)苯基)-1,3,2-二氧杂硼烷(67mg)产率75%。
4,4,5,5-四甲基-2-(3-三氟甲基-2-((苯硒基)甲基)苯基)-1,3,2-二氧杂硼烷的结构式如下:
4,4,5,5-四甲基-2-(3-三氟甲基-2-((苯硒基)甲基)苯基)-1,3,2-二氧杂硼烷的核磁共振氢谱和核磁共振碳谱如图4所示:1H NMR(600MHz,CDCl3)(600MHz,CDCl3)δ7.80-7.76(m,1H),7.47-7.43(m,1H),7.15-7.03(m,4H),4.54(s,2H),1.14(s,12H).13C NMR(151MHz,CDCl3)δ143.6,139.6,133.1,131.4,128.9,128.5(q,J=28.7Hz),128.2(q,J=6.0Hz),127.2,126.1,123.6(q,J=274.8Hz),84.3,27.6,24.9.HRMS(ESI):Calculatedfor C20H22BF3O2Se[M+Na]+:465.0725,Found:465.0722.
实施例5
合成4,4,5,5-四甲基-2-(3-甲基-2-((苯硒基)甲基)苯基)-1,3,2-二氧杂硼烷。
称取(1,5-环辛二烯)二氯化铱(I)二聚体(5.4mg,0.008mmol)三环己基膦(4.4mg,0.016mmol)加入史莱克管中,在惰性气体保护下,在80℃反应20min,加入双联硼酸频那醇酯(25.4mg,0.1mmol),加入(2-甲基苄基)(苯基)硒(52.4mg,0.2mmol)和频哪醇硼烷(200μL,13.6mmol)80℃搅拌反应24h。所得反应物用硅胶柱(石油醚/乙酸乙酯)纯化得到4,4,5,5-四甲基-2-(3-甲基-2-((苯硒基)甲基)苯基)-1,3,2-二氧杂硼烷(52mg)产率67%。
4,4,5,5-四甲基-2-(3-甲基-2-((苯硒基)甲基)苯基)-1,3,2-二氧杂硼烷的结构式如下:
4,4,5,5-四甲基-2-(3-甲基-2-((苯硒基)甲基)苯基)-1,3,2-二氧杂硼烷的核磁共振氢谱和核磁共振碳谱如图5所示:1H NMR(600MHz,CDCl3)δ7.66-7.62(m,1H),7.50-7.45(m,2H),7.24-7.16(m,4H),7.14-7.09(m,1H),4.60(s,2H),2.26(s,3H),1.30(s,12H).13CNMR(151MHz,CDCl3)δ143.0,136.7,134.3,133.7,133.3,131.6,128.9,127.1,126.4,83.7,29.1,24.9,19.8.HRMS(ESI):Calculated for C20H25BO2Se[M+Na]+:411.1005,Found:411.1003.
实施例6
合成4,4,5,5-四甲基-2-(2-(((苯硒基)甲基)-4-(三氟甲基)苯基)-1,3,2-二氧杂硼烷。
称取(1,5-环辛二烯)二氯化铱(I)二聚体(2.7mg,0.004mmol)三环己基膦(2.2mg,0.008mmol)加入史莱克管中,在惰性气体保护下,在80℃反应20min,加入双联硼酸频那醇酯(25.4mg,0.1mmol),加入(3-三氟甲基苄基)(苯基)硒(63.2mg,0.2mmol)和频哪醇硼烷(100μL,6.8mmol)80℃搅拌反应24h。所得反应物用硅胶柱(石油醚/乙酸乙酯)纯化得到4,4,5,5-四甲基-2-(2-(((苯硒基)甲基)-4-(三氟甲基)苯基)-1,3,2-二氧杂硼烷(70mg)产率80%。
4,4,5,5-四甲基-2-(2-(((苯硒基)甲基)-4-(三氟甲基)苯基)-1,3,2-二氧杂硼烷的结构式如下:
4,4,5,5-四甲基-2-(2-(((苯硒基)甲基)-4-(三氟甲基)苯基)-1,3,2-二氧杂硼烷的核磁共振氢谱和核磁共振碳谱如图6所示:1H NMR(600MHz,CDCl3)δ7.91-7.86(m,1H),7.41-7.38(m,1H),7.38-7.34(m,2H),7.28-7.18(m,3H),7.03(s,1H),4.42(s,2H),1.36(s,12H).13C NMR(151MHz,CDCl3)δ147.1,136.9,134.8,132.1(q,J=31.7Hz),129.9,129.0,127.8,125.8(q,J=3.0Hz),124.0(q,J=273.3Hz),122.5(q,J=3.0Hz),84.3,32.3,25.0.HRMS(ESI):Calculated for C20H22BF3O2Se[M+Na]+:465.0722,Found:465.0724.
实施例7
合成2-(4-溴-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷。
称取(1,5-环辛二烯)二氯化铱(I)二聚体(2.7mg,0.004mmol)三环己基膦(2.2mg,0.008mmol)加入史莱克管中,在惰性气体保护下,在80℃反应20min,加入双联硼酸频那醇酯(25.4mg,0.1mmol),加入(3-溴苄基)(苯基)硒(65.2mg,0.2mmol)和频哪醇硼烷(100μL,6.8mmol)80℃搅拌反应24h。所得反应物用硅胶柱(石油醚/乙酸乙酯)纯化得到2-甲基-1,2,3,4-四氢喹啉(63mg)产率69%。
2-(4-溴-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷的结构式如下:
2-(4-溴-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷的核磁共振氢谱和核磁共振碳谱如图7所示:1H NMR(600MHz,CDCl3)δ7.66-7.62(m,1H),7.43-7.39(m,2H),7.33-7.29(m,1H),7.28-7.21(m,3H),7.06(s,1H),4.36(s,2H),1.33(s,12H).13CNMR(151MHz,CDCl3)δ148.3,138.0,134.4,132.4,130.4,129.2,129.0,127.6,125.3,84.0,32.0,25.0.HRMS(ESI):Calculated for C19H22BBrO2Se[M+Na]+:474.9954,Found:474.9957.
实施例8
合成2-(3,4-二氟-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷。
称取(1,5-环辛二烯)二氯化铱(I)二聚体(2.7mg,0.004mmol)三环己基膦(2.2mg,0.008mmol)加入史莱克管中,在惰性气体保护下,在80℃反应20min,加入双联硼酸频那醇酯(25.4mg,0.1mmol),加入(2,3-二氟苄基)(苯基)硒(56.8mg,0.2mmol)和频哪醇硼烷(100μL,6.8mmol)80℃搅拌反应24h。所得反应物用硅胶柱(石油醚/乙酸乙酯)纯化得到2-(3,4-二氟-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷(64mg)产率78%。
2-(3,4-二氟-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷的结构式如下:
2-(3,4-二氟-2-(((苯硒基)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷的核磁共振氢谱和核磁共振碳谱如图8所示:1H NMR(600MHz,CDCl3)δ7.54-7.49(m,1H),7.47-7.43(m,2H),7.27-7.18(m,3H),7.00-6.92(m,1H),4.49(s,2H),1.31(s,12H).13C NMR(151MHz,CDCl3)δ152.2(dd,J=252.17Hz,J=13.6Hz),148.7(dd,J=249.2Hz,J=12.1Hz),136.0(d,J=9.1Hz),134.51,132.3(dd,J=7.6Hz,J=4.5Hz),130.1,128.9,127.7,114.9(d,J=16.6Hz),84.1,25.0,23.4.HRMS(ESI):Calculated for C19H22BF3O2Se[M+Na]+:433.0660,Found:433.0652.实施例9
合成2-(2-((((4-氟苯基)硒代)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷。
称取(1,5-环辛二烯)二氯化铱(I)二聚体(2.7mg,0.004mmol)三环己基膦(2.2mg,0.008mmol)加入史莱克管中,在惰性气体保护下,在80℃反应20min,加入双联硼酸频那醇酯(25.4mg,0.1mmol),加入(3-(三氟甲基)-4-氯苄基)(苯基)硒(70.0mg,0.2mmol)和频哪醇硼烷(100μL,6.8mmol)80℃搅拌反应24h。所得反应物用硅胶柱(石油醚/乙酸乙酯)纯化得到2-(2-((((4-氟苯基)硒代)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷(78mg)产率82%。
2-(2-((((4-氟苯基)硒代)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷的结构式如下:
2-(2-((((4-氟苯基)硒代)甲基)苯基)-4,4,5,5-四甲基-1,3,2-二氧杂硼烷的核磁共振氢谱和核磁共振碳谱如图9所示:1H NMR(600MHz,CDCl3)δ7.84(s,1H),7.35-7.30(m,2H),7.25-7.22(m,1H),7.21-7.16(m,2H),6.99(s,1H),4.33(s,2H),1.33(s,12H).13C NMR(151MHz,CDCl3)δ145.3,138.9,135.0,129.6,129.5,129.3(2C),129.1,128.1(q,J=4,5Hz),122.7(q,J=273.3Hz),119.95,84.6,31.6,25.0.HRMS(EI):Calculated forC20H22BF3O2Se[M]:476.0440,Found:476.0447.
实施例10
合成4,4,5,5-四甲基-2-(2-(((苯硒基)甲基)-4-(甲基)苯基)-1,3,2-二氧杂硼烷。
称取(1,5-环辛二烯)二氯化铱(I)二聚体(5.4mg,0.008mmol)三环己基膦(4.4mg,0.016mmol)加入史莱克管中,在惰性气体保护下,在80℃反应20min,加入双联硼酸频那醇酯(25.4mg,0.1mmol),加入(3-甲基苄基)(苯基)硒(52.4mg,0.2mmol)和频哪醇硼烷(200μL,13.6mmol)80℃搅拌反应24h。所得反应物用硅胶柱(石油醚/乙酸乙酯)纯化得到4,4,5,5-四甲基-2-(2-(((苯硒基)甲基)-4-(甲基)苯基)-1,3,2-二氧杂硼烷(58mg)产率75%。
4,4,5,5-四甲基-2-(2-(((苯硒基)甲基)-4-(甲基)苯基)-1,3,2-二氧杂硼烷的结构式如下:
4,4,5,5-四甲基-2-(2-(((苯硒基)甲基)-4-(甲基)苯基)-1,3,2-二氧杂硼烷的核磁共振氢谱和核磁共振碳谱如图10所示:1H NMR(600MHz,CDCl3)δ7.74-7.65(m,1H),7.49-7.41(m,2H),7.26-7.16(m,3H),7.01(s,1H),6.83(s,1H),4.45(s,2H),2.24(s,3H),1.34(s,12H).13C NMR(151MHz,CDCl3)δ145.8,140.9,136.7,133.9,131.4,130.5,128.8,127.1,127.0,83.6,32.6,25.0,21.6.HRMS(ESI):Calculated for C20H25BO2Se[M+Na]+:411.1005,Found:411.1007.
实施例11
合成4,4,5,5-四甲基-2-(2-((甲基硒基)甲基)苯基)-1,3,2-二氧杂硼烷。
称取(1,5-环辛二烯)二氯化铱(I)二聚体(5.4mg,0.008mmol)三环己基膦(4.4mg,0.016mmol)加入史莱克管中,在惰性气体保护下,在80℃反应20min,加入双联硼酸频那醇酯(5.1mg,0.02mmol),加入苄基(甲基)硒(37.2mg,0.2mmol)和频哪醇硼烷(200μL,13.6mmol)80℃搅拌反应24h。所得反应物用硅胶柱(石油醚/乙酸乙酯)纯化得到4,4,5,5-四甲基-2-(2-((甲基硒基)甲基)苯基)-1,3,2-二氧杂硼烷产率37%。
4,4,5,5-四甲基-2-(2-((甲基硒基)甲基)苯基)-1,3,2-二氧杂硼烷的结构式如下:
4,4,5,5-四甲基-2-(2-((甲基硒基)甲基)苯基)-1,3,2-二氧杂硼烷的核磁共振氢谱和核磁共振碳谱如图11所示:1H NMR(400MHz,CDCl3)δδ7.72(d,J=7.3Hz,1H),7.29-7.23(m,1H),7.15-7.08(m,2H),4.00(s,2H),1.80(s,3H),1.29(s,12H).13C NMRδ146.8,136.5,130.7,129.4,126.0,83.8,28.4,25.0,4.3.HRMS(ESI):Calculated for C14H21BO2Se[M+Na]+:335.0692,Found:335.0692.
实施例12
合成2,2'-(5-氟-2-((苯硒基)甲基)-1,3-亚苯基)双(4,4,5,5-四甲基-1,3,2-二氧杂硼烷)。
称取(1,5-环辛二烯)二氯化铱(I)二聚体(5.4mg,0.008mmol)三环己基膦(4.4mg,0.016mmol)加入史莱克管中,在惰性气体保护下,在80℃反应20min,加入双联硼酸频那醇酯(25.4mg,0.1mmol),加入(4-氟苄基)(苯基)硒(53.2mg,0.2mmol)和频哪醇硼烷(200μL,13.6mmol)80℃搅拌反应24h。所得反应物用硅胶柱(石油醚/乙酸乙酯)纯化得到2,2'-(5-氟-2-((苯硒基)甲基)-1,3-亚苯基)双(4,4,5,5-四甲基-1,3,2-二氧杂硼烷)产率70%。
2,2'-(5-氟-2-((苯硒基)甲基)-1,3-亚苯基)双(4,4,5,5-四甲基-1,3,2-二氧杂硼烷)的结构式如下:
2,2'-(5-氟-2-((苯硒基)甲基)-1,3-亚苯基)双(4,4,5,5-四甲基-1,3,2-二氧杂硼烷)的核磁共振氢谱和核磁共振碳谱如图12所示:1H NMR(600MHz,CDCl3)δ7.50-7.46(m,2H),7.37-7.33(m,2H),7.23-7.14(m,3H),4.91(s,2H),1.27(s,24H).13C NMR(151MHz,CDCl3)δ160.6(d,J=247.6Hz),148.3,134.2,131.3,128.7,127.1,124.7(d,J=19.6Hz),84.0,30.1,24.9.m.p.:99-101℃.HRMS(ESI):Calculated for C25H33B2FO4Se[M+Na]+:541.1606,Found:541.1605。
Claims (9)
1.一种基于硒导向碳氢键硼化快速制备苄基硒类化合物的方法,包括如下步骤:
(1)将铱催化剂和配体加入史莱克管中,在惰性气体保护下,加入溶剂,在一定温度下搅拌20min;将装有催化剂和配体络合物的史莱克管中加入硼源,底物,添加剂;反应过程中用TLC进行跟踪以决定具体的反应时间;合成路线为:
(2)反应结束后,将步骤(1)中有机溶剂旋干,用柱层析进行纯化得到有机硒硼化产物,洗脱剂为石油醚和乙酸乙酯的混合溶液;
所述铱催化剂为(1,5-环辛二烯)二氯化铱(I)二聚体;
所述配体为三苯基膦,三环己基膦,3-(五氟)环己基膦或者三丁基膦;
所述硼源为频那醇硼烷;
所述添加剂为双联硼频哪醇酸酯;
R1选自氢、卤素、烷基;
R2选自烷基、芳基;
R1和R2相同或不同。
2.如权利要求1所述的一种基于硒导向碳氢键硼化快速制备苄基硒类化合物的方法,其特征在于:反应温度为20-200℃,反应时间为0.5h~48h。
3.如权利要求1所述的一种基于硒导向碳氢键硼化快速制备苄基硒类化合物的方法,其特征在于:含硒化合物为苄基苯基硒及衍生物,含硒化合物在溶剂中的摩尔浓度为0.01~10mmol/mL。
4.如权利要求1所述的一种基于硒导向碳氢键硼化快速制备苄基硒类化合物的方法,其特征在于:反应溶剂为四氢呋喃、二氯甲烷、二氯乙烷、甲苯、1,4-二氧六环、乙腈、乙酸乙酯、苯、正己烷中的一种或一种以上混合。
5.如权利要求1所述的一种基于硒导向碳氢键硼化快速制备苄基硒类化合物的方法,其特征在于:配体用量为2%~100%。
6.如权利要求1所述的一种基于硒导向碳氢键硼化快速制备苄基硒类化合物的方法,其特征在于:铱催化剂的用量为1%~50%。
7.如权利要求1所述的一种基于硒导向碳氢键硼化快速制备苄基硒类化合物的方法,其特征在于:所述硼源用量为0.5~10当量。
8.如权利要求1所述的一种基于硒导向碳氢键硼化快速制备苄基硒类化合物的方法,其特征在于:添加剂用量为0.5~25当量。
9.如权利要求1所述的一种基于硒导向碳氢键硼化快速制备苄基硒类化合物的方法,其特征在于:柱层析选择200~300目的硅胶或碱性氧化铝作为固定相,洗脱剂选择石油醚和乙酸乙酯的混合体系。
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