CN111943967B - 一种合成烯基硼酸酯类化合物的方法 - Google Patents
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- ARAINKADEARZLZ-ZHACJKMWSA-N 4,4,5,5-tetramethyl-2-[(e)-2-phenylethenyl]-1,3,2-dioxaborolane Chemical compound O1C(C)(C)C(C)(C)OB1\C=C\C1=CC=CC=C1 ARAINKADEARZLZ-ZHACJKMWSA-N 0.000 description 1
- 125000004861 4-isopropyl phenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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- Y02P20/584—Recycling of catalysts
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Abstract
本发明属于化学合成领域,具体涉及一种合成烯基硼酸酯类化合物的方法,在钴金属催化剂的作用下,式(Ⅰ)所示的烯烃类化合物和联硼酸酯在有机溶剂中反应得到式(Ⅱ)烯基硼酸酯类化合物。本方法从稳定、廉价易得的烯烃和联硼酸酯出发,使用廉价的钴金属催化剂,发展高效的烯烃脱氢硼化反应,反应的副产物为氢气,原子经济性高,产物为单一的E‑构型产物。
Description
技术领域
本发明属于化学合成领域,具体涉及一种合成烯基硼酸酯类化合物的方法。
背景技术
有机硼化合物是合成化学中最重要的中间体之一,可以转化为几乎所有类型的官能团化合物,广泛应用于科学研究和工业大生产中。烯基硼化合物由于分子中双键的存在,容易进行进一步转化,因此烯基硼化合物的合成方法研究受到了合成化学领域的广泛关注。
传统的烯基硼化合物的方法是以炔烃或烯基卤化物为原料,使用当量的金属试剂,通过碳-金属化,氢-金属化等转化为相应的烯基金属中间体,最后和硼试剂反应得到产物,其化学式为:
近期发展的过渡金属催化炔烃的硼氢化反应以炔烃为原料,是合成烯基硼化合物的高效方法,但是炔烃不易制备,价格昂贵,其化学式为:
因此,需要一种经济效益更好的合成方法。
发明内容
本发明的目的是为了克服现有技术存在的缺点和不足,而提供一种合成烯基硼酸酯类化合物的方法。
本发明所采取的技术方案如下:一种合成烯基硼酸酯类化合物的方法,在钴金属催化剂的作用下,式(Ⅰ)所示的烯烃类化合物和联硼酸酯在有机溶剂中反应得到式(Ⅱ)烯基硼酸酯类化合物;
其中R1选自烷基、芳基或芳香类杂环中的一种,R2为H。
反应体系中还有碱、配体添加剂。
所述配体添加剂为式(Ⅲ)所示的化合物或PNN或PNP;
R为苄基、甲基、乙基、异丙基、叔丁基、苯基、二甲基中的一种。
所述配体添加剂为式(Ⅲ)所示的化合物,R为Bn。
所述碱为KOtBu、NaOtBu、LiOtBu、K2CO3、K3PO4、Cs2CO3中的一种或多种。
在氩气或氮气保护下,在反应容器中加入钴金属催化剂、配体添加剂和有机溶剂,室温下搅拌,然后依次加入式(Ⅰ)所示的烯烃类化合物、联硼酸酯和碱,加热到60-70℃下反应至反应结束。
反应结束后,除去溶剂,然后柱层析分离,得到纯化的产物。
本发明的有益效果如下:本方法从稳定、廉价易得的烯烃和联硼酸酯出发,使用廉价的钴金属催化剂,发展高效的烯烃脱氢硼化反应,反应的副产物为氢气,原子经济性高,产物为单一的E-构型产物。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚,下面将对本发明作进一步地详细描述。
实施例1:
将加入搅拌子的10mL Schlenk反应管用热风枪加热并同时使用油泵抽气,冷却至室温后,反复抽氩气冲氩气三次,在充满氩气的条件下,依次加入CoCl2(0.025mmol),配体添加剂(0.03mmol)和THF(1mL),在室温下搅拌5min,随后依次加入烯烃1a(0.75mmol),B2pin2(0.50mmol)和碱。将反应混合物加热并在65℃搅拌3h。反应结束后将溶液用乙酸乙酯稀释并转移至茄形瓶中,减压旋蒸除去溶剂,接着用200-300目硅胶快速柱层析,使用100:1PE/EtOAc至10:1PE/EtOAc的淋洗剂洗脱得到产物2a。
配体添加剂的选择、碱的选择及使用量、纯化收率如表1所示。可以看出配体添加剂的选择、碱的选择及使用量对产物的合成影响较大。配体添加剂选择PNBnN、PNMeN、PNEtN、PNPhN、PNN,产物的收率可以达到80%以上,其中,同等条件下,PNBnN效果最优。在加入15mol%的碱的条件下,发现选择KOtBu、NaOtBu、LiOtBu、K2CO3、K3PO4、Cs2CO3均可达到较优的收率,Na2CO3效果较差。增加碱的用量到50%,收率可以提高到99%。
表1实施例1条件优化对比
实施例2:
将加入搅拌子的10mL Schlenk反应管用热风枪加热并同时使用油泵抽气,冷却至室温后,反复抽氩气冲氩气三次,在充满氩气的条件下,依次加入CoCl2(0.0125mmol),PABnO(0.015mmol)和THF(1mL),在室温下搅拌5min,随后依次加入烯烃1(0.75mmol),B2pin2(0.50mmol)和K2CO3(0.25mmol)。将反应混合物加热并在65℃搅拌3h。反应结束后将溶液用乙酸乙酯稀释并转移至茄形瓶中,减压旋蒸除去溶剂,接着用200-300目硅胶快速柱层析,使用100:1PE/EtOAc至10:1PE/EtOAc的淋洗剂洗脱得到产物2。
如表2所示,选择不同的底物烯烃1可以得到不同的产物2,高收率且高选择性。
表2不同的底物烯烃1反应得到的产物2及收率
实施例3:
将加入搅拌子的10mL Schlenk反应管用热风枪加热并同时使用油泵抽气,冷却至室温后,反复抽氩气冲氩气三次,在充满氩气的条件下,依次加入CoCl2(0.0125mmol),PAiPrO(0.015mmol)和THF(1mL),在室温下搅拌5min,随后依次加入烯烃1u(0.5mmol),B2pin2(1.0mmol)和K2CO3(0.25mmol)。将反应混合物加热并在65℃搅拌3h。反应结束后将溶液用乙酸乙酯稀释并转移至茄形瓶中,减压旋蒸除去溶剂,接着用200-300目硅胶快速柱层析,使用100:1PE/EtOAc至10:1PE/EtOAc的淋洗剂洗脱得到产物。
实施例4:
将加入搅拌子的25mL Schlenk反应管用热风枪加热并同时使用油泵抽气,冷却至室温后,反复抽氩气冲氩气三次,在充满氩气的条件下,依次加入CoCl2(0.005mmol),L-Bn(0.006mmol)和超干THF(10mL),在室温下搅拌5min,随后依次加入烯烃(7.5mmol),B2pin2(5.0mmol)和K2CO3(2.5mmol)。将反应混合物加热并在65℃搅拌12h。反应结束后将溶液用乙酸乙酯稀释并转移至茄形瓶中,减压旋蒸除去溶剂,接着用200-300目硅胶快速柱层析,使用100:1PE/EtOAc至10:1PE/EtOAc的淋洗剂洗脱得到产物。
以上实施例所制备得到的产物的表征数据如下:
2a(E)-2-(4-methoxystyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane.无色油状液体,1H NMR(CDCl3,400MHz):δ7.44(d,J=8.8Hz,2H),7.35(d,J=18.4Hz,1H),6.87(d,J=8.8Hz,2H),6.02(d,J=18.4Hz,1H),3.81(s,3H),1.31(s,12H).
3-2b(E)-2-(3-methoxystyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane,淡黄色油状液体,1H NMR(CDCl3,400MHz):δ7.37(d,J=18.6Hz,1H),7.29-7.23(m,1H),7.09(d,J=7.6Hz,1H),7.05-7.01(m,1H),6.88-6.83(m,1H),6.16(d,J=18.6Hz,1H),3.81(s,3H),1.32(s,12H).
2c(E)-2-(2-methoxystyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane,无色油状液体,1H NMR(CDCl3,400MHz):δ7.78(d,J=18.6Hz,1H),7.57-7.53(m,1H),7.30-7.23(m,1H),6.96-6.91(m,1H),6.89-6.85(m,1H),6.18(d,J=18.6Hz,1H),3.85(s,3H),1.31(s,12H).
2d(E)-4,4,5,5-tetramethyl-2-styryl-1,3,2-dioxaborolane,无色油状液体,1H NMR(CDCl3,400MHz):δ7.52-7.46(m,2H),7.40(d,J=18.6Hz,1H),7.37-7.28(m,3H),6.17(d,J=18.6Hz,1H),1.32(s,12H).
2e(E)-4,4,5,5-tetramethyl-2-(4-methylstyryl)-1,3,2-dioxaborolane,黄色固体,1H NMR(CDCl3,400MHz):δ7.42-7.33(m,3H),7.14(d,J=7.8Hz,2H),6.11(d,J=18.4Hz,1H),2.35(s,3H),1.31(s,12H).
2f(E)-2-(4-ethylstyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane,无色油状液体,1H NMR(CDCl3,400MHz):δ7.44-7.34(m,3H),7.20-7.14(m,2H),6.12(d,J=18.4Hz,1H),2.64(q,J=7.6Hz,2H),1.31(s,12H),1.23(t,J=7.6Hz,3H).
2g(E)-2-(4-isopropylstyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane,淡黄色油状液体,1H NMR(CDCl3,400MHz):δ7.45-7.34(m,3H),7.20(d,J=8.2Hz,2H),6.11(d,J=18.6Hz,1H),2.94-2.85(m,1H),1.31(s,12H),1.24(d,J=7.0Hz,6H).
2h(E)-2-(4-(tert-butyl)styryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane,淡黄色油状液体,1H NMR(CDCl3,400MHz):δ7.46-7.33(m,5H),6.12(d,J=18.6Hz,1H),1.31(s,21H).
2i(E)-N,N-dimethyl-4-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)vinyl)aniline,黄绿色油状液体,1H NMR(CDCl3,400MHz):δ7.39(d,J=8.8Hz,2H),7.33(d,J=18.4Hz,1H),6.66(d,J=8.8Hz,2H),5.92(d,J=18.4Hz,1H),2.98(s,6H),1.30(s,12H).
2j(E)-tert-butyldimethyl(4-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)vinyl)phenoxy)silane,无色油状液体,1H NMR(CDCl3,400MHz):δ7.40-7.31(m,3H),6.80(d,J=8.8Hz,2H),6.01(d,J=18.6Hz,1H),1.31(s,12H),0.97(s,9H),0.20(s,6H).
2k(E)-2-(4-fluorostyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane,淡黄色油状液体,1H NMR(CDCl3,500.1MHz):δ7.50-7.42(m,2H),7.35(d,J=18.4Hz,1H),7.07-6.98(m,2H),6.07(d,J=18.4Hz,1H),1.31(s,12H).
2l(E)-2-(4-chlorostyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane,淡黄色油状液体,1H NMR(CDCl3,400MHz):δ7.43-7.38(m,2H),7.37-7.28(m,3H),6.16(d,J=18.4Hz,1H),1.31(s,12H).
2m(E)-2-(3-chlorostyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane,无色油状液体,1H NMR(CDCl3,400MHz):δ7.45(s,1H),7.37-7.24(m,4H),6.17(d,J=18.6Hz,1H),1.31(s,12H).
2n(E)-2-(3-bromostyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane,无色油状液体,1H NMR(CDCl3,400MHz):δ7.63-7.59(m,1H),7.43-7.37(m,2H),7.30(d,J=18.4Hz,1H),7.22-7.17(m,1H),6.16(d,J=18.4Hz,1H),1.31(s,12H).
2o(E)-4,4,5,5-tetramethyl-2-(4-(trifluoromethyl)styryl)-1,3,2-dioxaborolane,淡黄色油状液体,1H NMR(CDCl3,400MHz):δ7.62-7.54(m,4H),7.40(d,J=18.4Hz,1H),6.26(d,J=18.4Hz,1H),1.32(s,12H).
2p(E)-2-(2,4-dimethoxystyryl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane,无色油状液体,1H NMR(CDCl3,400MHz):δ7.69(d,J=18.6Hz,1H),7.49(d,J=8.6Hz,1H),6.48(dd,J=2.4,8.6Hz,1H),6.43-6.40(m,1H),6.06(d,J=18.6Hz,1H),3.84-3.80(m,6H),1.30(s,12H);13C NMR(125.8MHz,CDCl3):δ161.5,158.6,143.8,128.1,119.8,104.9,98.2,83.0,55.3,25.0,24.8.
2q(E)-4,4,5,5-tetramethyl-2-(3,4,5-trimethoxystyryl)-1,3,2-dioxaborolane,无色油状液体,1H NMR(CDCl3,400MHz):δ7.32(d,J=18.4Hz,1H),6.74(s,2H),6.07(d,J=18.4Hz,1H),3.86(s,9H),1.32(s,12H).
2r(E)-4,4,5,5-tetramethyl-2-(2-(naphthalen-1-yl)vinyl)-1,3,2-dioxaborolane,无色油状液体,1H NMR(CDCl3,400MHz):δ8.29-8.17(m,2H),7.87-7.80(m,2H),7.74(d,J=7.2Hz,1H),7.56-7.44(m,3H),6.27(d,J=18.2Hz,1H),1.35(s,12H).
2s(E)-3-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)vinyl)pyridine,无色油状液体,1H NMR(CDCl3,400MHz):δ8.71-8.66(m,1H),8.55-8.49(m,1H),7.83-7.78(m,1H),7.38(d,J=18.6Hz,1H),7.31-7.26(m,1H),6.25(d,J=18.6Hz,1H),1.32(s,12H).
2t methyl(E)-4-(2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)vinyl)benzoate,无色油状液体,1H NMR(CDCl3,400MHz):δ8.00(d,J=8.2Hz,2H),7.53(d,J=8.2Hz,2H),7.41(d,J=18.4Hz,1H),6.27(d,J=18.4Hz,1H),3.91(s,3H),1.32(s,12H).
2u(E)-4,4,5,5-Tetramethyl-2-(2-phenylprop-1-en-1-yl)-1,3,2-dioxaborolane,无色油状液体,1H NMR(CDCl3,500MHz):δ7.51-7.49(m,2H),7.33-7.25(m,3H),5.76(s,1H),2.41(s,3H),1.31(s,12H).
以上所揭露的仅为本发明较佳实施例而已,当然不能以此来限定本发明之权利范围,因此依本发明权利要求所作的等同变化,仍属本发明所涵盖的范围。
Claims (1)
1.一种合成烯基硼酸酯类化合物的方法,其特征在于:在CoCl2作为催化剂的作用下,式(Ⅰ)所示的烯烃类化合物和联硼酸酯,在有机溶剂中反应得到式(Ⅱ)所示烯基硼酸酯类化合物;
所述碱为K2CO3,其用量为联硼酸酯的50 mol%;所述联硼酸酯为B2pin2;
其制备过程为:在氩气或氮气保护下,在反应容器中加入金属催化剂、配体添加剂和有机溶剂,室温下搅拌,然后依次加入式(Ⅰ)、(Ⅱ)、(Ⅲ)中所示的烯烃类化合物、联硼酸酯和碱,加热到60-70℃下反应至反应结束,反应结束后,除去溶剂,然后柱层析分离,得到纯化的产物。
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Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103962183A (zh) * | 2013-02-04 | 2014-08-06 | 中国科学院上海有机化学研究所 | 一种pnn配体-金属络合物催化剂及其制备方法和应用 |
EP2857405A1 (en) * | 2013-10-01 | 2015-04-08 | Studiengesellschaft Kohle mbH | Process for the trans-selective hydroboration of internal alkynes |
CN105153229A (zh) * | 2015-06-18 | 2015-12-16 | 武汉凯特立斯科技有限公司 | 一种手性三齿pnn配体及其在不对称氢化反应中的应用 |
CN105665025A (zh) * | 2014-01-07 | 2016-06-15 | 中国科学院上海有机化学研究所 | 一种pnn配体-钴络合物催化剂及其制备方法和应用 |
CN109232630A (zh) * | 2018-10-23 | 2019-01-18 | 上海交通大学 | 一种铜催化的烯基硼酯的合成方法 |
CN109529940A (zh) * | 2018-12-11 | 2019-03-29 | 温州大学 | 二苯胺-膦-噁唑啉配体、其合成方法及其金属配合物和用途 |
CN110878001A (zh) * | 2019-11-29 | 2020-03-13 | 温州大学 | (z)-烯烃异构化转化为(e)-烯烃的方法 |
-
2020
- 2020-08-14 CN CN202010822813.4A patent/CN111943967B/zh active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103962183A (zh) * | 2013-02-04 | 2014-08-06 | 中国科学院上海有机化学研究所 | 一种pnn配体-金属络合物催化剂及其制备方法和应用 |
EP2857405A1 (en) * | 2013-10-01 | 2015-04-08 | Studiengesellschaft Kohle mbH | Process for the trans-selective hydroboration of internal alkynes |
CN105665025A (zh) * | 2014-01-07 | 2016-06-15 | 中国科学院上海有机化学研究所 | 一种pnn配体-钴络合物催化剂及其制备方法和应用 |
CN105153229A (zh) * | 2015-06-18 | 2015-12-16 | 武汉凯特立斯科技有限公司 | 一种手性三齿pnn配体及其在不对称氢化反应中的应用 |
CN109232630A (zh) * | 2018-10-23 | 2019-01-18 | 上海交通大学 | 一种铜催化的烯基硼酯的合成方法 |
CN109529940A (zh) * | 2018-12-11 | 2019-03-29 | 温州大学 | 二苯胺-膦-噁唑啉配体、其合成方法及其金属配合物和用途 |
CN110878001A (zh) * | 2019-11-29 | 2020-03-13 | 温州大学 | (z)-烯烃异构化转化为(e)-烯烃的方法 |
Non-Patent Citations (2)
Title |
---|
Bulky rhodium diimine complexes for the catalyzed borylation of vinylarenes;S.J. Geier et al.;《Inorganic Chemistry Communications》;20061231;第9卷;第788-791页 * |
PSiP-Pincer Type Palladium-Catalyzed Dehydrogenative Borylation of Alkenes and 1,3-Dienes;Naohiro Kirai et al.;《Bull. Chem. Soc. Jpn.》;20131231;第86卷(第7期);第784-799页 * |
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