CN110423247A - 一种制备α-烯基硅烷类化合物的方法 - Google Patents
一种制备α-烯基硅烷类化合物的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 150000001875 compounds Chemical class 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 26
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 25
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical class [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000077 silane Inorganic materials 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 pyridine imine Chemical class 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003446 ligand Substances 0.000 claims abstract description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 14
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 150000001868 cobalt Chemical class 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 239000003480 eluent Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical group 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
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- 238000006555 catalytic reaction Methods 0.000 abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 abstract description 7
- 239000010941 cobalt Substances 0.000 abstract description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000012190 activator Substances 0.000 abstract description 5
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- 238000007796 conventional method Methods 0.000 abstract description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 44
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 19
- 239000007788 liquid Substances 0.000 description 12
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- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 description 9
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
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- 238000005352 clarification Methods 0.000 description 2
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- 238000010471 Markovnikov's rule Methods 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
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- 150000001336 alkenes Chemical class 0.000 description 1
- 238000013459 approach Methods 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
- 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
- C07F7/0896—Compounds with a Si-H linkage
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Abstract
一种制备α‑烯基硅烷类化合物的方法,所述方法为:在惰性气体保护下,将炔烃、硅烷、钴盐、吡啶亚胺类双齿氮配体、反应溶剂混合,于30~60℃下反应1~10h,之后经后处理,得到α‑烯基硅烷类化合物;本发明利用新型的吡啶亚胺类双齿配体提供了一种有效的钴催化炔烃氢硅化反应制备α‑烯基硅烷类化合物的方法,与现有方法相比,该方法无需采用催化剂活化剂,操作简单,反应条件温和。反应底物适用范围广,选择性高,催化效率高,在合成上具有较大的实际应用价值。
Description
(一)技术领域
本发明涉及一种α-烯基硅烷类化合物的制备方法,具体涉及一种利用新型吡啶亚胺类双齿氮配体,钴催化炔烃马氏规则区域选择性的氢硅化反应制备α-烯基硅烷类化合物的方法。
(二)背景技术
有机硅在有机合成中是重要的合成砌块,在功能材料和药物研发中也具有潜在价值。在众多的硅烷产物中,烯基硅烷是多功能的合成结构单元,因为它们稳定,易于处理,无毒,并且倾向于进行各种转化。[a)T.A.Blumenkopf,L.E.Overman,Chem.Rev.1986,86,857;b)E.Langkopf,D.Schinzer,Chem.Rev.1995,95,1375.]。
过渡金属催化的炔烃的氢硅化反应是合成烯基硅烷的最高效的途径之一,具有原子利用率高、原料简单易得的特点[a)Angew.Chem.Int.Ed.2004,43,2749;b)Synthesis2005,853;c)Synthesis 2012,983.]。最近,利用丰富廉价的铁、钴和镍配合物催化烯烃氢硅化反应得到了快速发展[ACS Catalysis,2017,7(2):1227-1243.]。
钴作为环境友好、生物兼容性好的廉价过渡金属用于催化氢硅化反应得到了许多关注。其中,钴催化的炔烃的马氏加成氢硅化反应制备α-烯基硅烷类化合物的报道目前很少[a)Angew.Chem.,Int.Ed.2016,55,10835-10838;b)Angew.Chem.,Int.Ed.2016,55,10839-10843;c)Org.Lett.2018,20,6265-6269.]。这些现有的方法仍然存在一些问题,如:1、催化剂用量大。目前,最高的TON为1011[Org.Lett.2018,20,6265-6269.];2、已报道的方法均需要添加催化剂的活化剂,如三乙基硼氢化钠;3、反应体系对某些底物不能很好的兼容,如对烷基炔的氢硅化反应没有区域选择性[Org.Lett.2018,20,6265-6269];对二芳炔的氢硅化反应,收率仅为33%[Angew.Chem.,Int.Ed.2016.];4、目前已有的催化体系,不能同时兼容苯硅烷和二苯硅烷。因此,开发新型配体实现高效的钴催化的炔烃的马氏氢硅化反应具有重要的意义。
(三)发明内容
本发明的目的是提供一种有效的合成α-烯基硅烷类化合物的方法,该方法的催化体系化学选择性和区域选择性高,底物兼容性广,催化效率高,无需催化剂活化剂,操作简单。
本发明的技术方案如下:
一种制备α-烯基硅烷类化合物的方法,所述方法为:
在惰性气体保护下,将炔烃、硅烷、钴盐、吡啶亚胺类双齿氮配体(ICmPy)、反应溶剂混合,于30~60℃下反应1~10h,之后经后处理,得到α-烯基硅烷类化合物;
其中,炔烃为原料,硅烷为硅源,钴盐和吡啶亚胺类双齿氮配体原位生成的配合物为催化剂;
所述炔烃、硅烷、钴盐、吡啶亚胺类双齿氮配体的物质的量之比为1:1.2~1.5:0.0002~0.04:0.00025~0.05;
所述反应溶剂可选自:四氢呋喃、乙醚、苯、甲苯、乙酸乙酯、二氯甲烷、乙腈、石油醚、正己烷或N,N-二甲基甲酰胺,优选四氢呋喃;
所述反应溶剂的体积用量以炔烃的物质的量计为2~5mL/mmol;
所述后处理的方法为:反应结束后,待反应液冷却至室温(20~30℃),浓缩,硅胶柱层析分离,以石油醚为洗脱剂,收集含目标化合物的洗脱液,蒸除溶剂并干燥,得到α-烯基硅烷类化合物。
本发明中,
所述钴盐为CoX2,其中X为卤素、OAc、acac或OTf;
所述炔烃的结构式为其中R1、R2各自独立为芳基、杂芳基、烷基或氢;
所述硅烷的结构式为R15R16R17SiH,其中R15、R16、R17各自独立为氢、烷基、烷氧基或芳基;
所述吡啶亚胺类双齿氮配体的结构式为其中R18为氢、烷基、芳基、萘基或烷氧基,R19为烷基、芳基或萘基,R20、R21各自独立为氢或烷基。
本发明中,
术语“芳基”表示“杂芳基”表示 其中,Y为N、O或S,R3~R14各自独立为氢、卤素、烷基、烷氧基、氨基、羟基、氰基或芳基;
“烷基”表示C1~C6烷基;
“烷氧基”表示C1~C6烷氧基。
本发明的有益效果如下:
本发明利用新型的吡啶亚胺类双齿配体提供了一种有效的钴催化炔烃氢硅化反应制备α-烯基硅烷类化合物的方法。与现有方法相比,该方法无需采用催化剂活化剂,操作简单,反应条件温和。反应底物适用范围广,选择性高,催化效率高,在合成上具有较大的实际应用价值。
(四)具体实施方式
下面通过具体实施例对本发明的技术方案作进一步地详细描述,但本发明的保护范围并不仅限于此。
以下实施例中用到的配体结构式为:
实施例1:Co-ICmPy催化的末端炔烃与苯硅烷的马氏氢硅化反应:
在惰性氛围下,反应管中依次加入炔烃底物1mmol,苯硅烷1.5mmol,1mL THF和1mL已溶清催化剂溶液(配体:19.3mg,0.06mmol;Co(OAc)2:8.9mg,0.05mmol;THF:10.0mL),并将得到的混合物在室温下搅拌3小时,转出手套箱。30℃水浴下反应2h,反应体系冷却至室温,浓缩,粗产物快速硅胶柱层析得到最终产物。
P1:Pheny(1-phenylvinyl)silane
(原料为)
无色油状液体,收率:83%。1H NMR(500MHz,CDCl3)δ7.64(dd,J=7.7,5Hz,2H),7.52-7.34(m,8H),6.29(d,J=1Hz,1H),6.29(d,J=2.3Hz,1H),5.89(s,2H);
P2:phenyl(1-(o-tolyl)vinyl)silane
(原料为)
无色油状液体,收率:91%。1H NMR(500MHz,CDCl3)δ7.56(dd,J=7.9,1.4Hz,2H),7.42-7.32(m,3H),7.17-7.08(m,3H),6.99-6.96(m,1H),5.93(d,J=3.0Hz,1H),5.88(d,J=3.0Hz,1H),4.71(s,2H),2.26(s,3H).
P3:phenyl(1-(m-tolyl)vinyl)silane
(原料为)
无色油状液体,收率:83%。1H NMR(500MHz,CDCl3)δ7.61(dd,J=7.9,1.4Hz,2H),7.41-7.33(m,3H),7.21-7.15(m,3H),7.06(d,J=7.1Hz,1H),6.24(d,J=2.3Hz,1H),5.81(d,J=2.4Hz,1H),4.84(s,2H),2.35(s,3H).
P4:Phenyl(1-(P–tolyl)vinyl)silane
(原料为)
无色油状液体,收率:96%。1H NMR(500MHz,CDCl3)δ7.58(dd,J=7.9,1.4Hz,2H),7.40-7.33(m,3H),7.27(d,J=8.1Hz,2H),7.11(d,J=7.9Hz,2H),6.22(d,J=2.3Hz,1H),5.78(d,J=2.3Hz,1H),4.81(s,2H),2.32(s,3H).
P5:(1-(4-methoxyphenyl)vinyl)(phenyl)silane
(原料为)
无色油状液体,收率:90%。1H NMR(500MHz,CDCl3)δ7.61(dd,J=7.8,1.3Hz,87H),7.42-7.34(m,5H),6.88-6.84(m,2H),6.20(d,J=2.3Hz,1H),5.77(d,J=2.2Hz,1H),4.84(s,2H),3.80(s,3H).
P6:(1-([1,1'-biphenyl]-4-yl)vinyl)(phenyl)silane
(原料为)
白色固体,收率:92%。1H NMR(500MHz,CDCl3)δ7.66-7.54(m,6H),7.49-7.33(m,8H),6.31(d,J=2.2Hz,1H),5.88(d,J=2.3Hz,1H),4.89(s,2H).
P7:4-(1-(phenylsilyl)vinyl)benzonitrile
(原料为)
无色油状液,收率:96%。1H NMR(500MHz,CDCl3)δ7.60-7.54(m,4H),7.45-7.34(m,5H),6.26(d,J=1.9Hz,1H),5.96(d,J=2.0Hz,1H),4.82(s,2H).
P8:1,4-bis(1-(phenylsilyl)vinyl)benzene
(原料为)
白色固体,收率:74%。1H NMR(500MHz,CDCl3)δ7.58(d,J=7.8Hz,4H),7.41-7.33(m,6H),7.32(s,4H),6.24(d,J=2.3Hz,2H),5.81(d,J=2.3Hz,2H),4.81(s,2H).13C NMR(126MHz,CDCl3)δ143.78,141.38,135.74,131.30,131.21,130.05,128.28,126.78.HRMS-EI(m/z):Calc.for C22H22Si2[M]+342.1260,found 342.1273.
P9:3-(1-(phenylsilyl)vinyl)pyridine
(原料为)
浅黄色油状液体,收率:82%。1H NMR(500MHz,CDCl3)δ8.59(d,J=1.8Hz,1H),8.46(dd,J=4.8,1.3Hz,1H),7.64-7.55(m,3H),7.42-7.33(m,3H),7.23-7.19(m,1H),6.25(d,J=2.1Hz,1H),5.93(d,J=2.1Hz,1H),4.83(s,2H).
P10:2-(1-(phenylsilyl)vinyl)pyridine
(原料为)
无色油状液体,收率:97%。1H NMR(500MHz,CDCl3)δ8.58(d,J=4.8Hz,1H),7.72-7.68(d,J=7.8Hz,2H),7.66-7.61(m,1H),7.58-7.54(m,1H),7.41-7.33(m,3H),7.15-7.11(m,1H),6.62(d,J=1.8Hz,1H),5.99(d,J=1.8Hz,1H),4.88(s,2H).13C NMR(126MHz,CDCl3)δ159.60,149.07,145.63,136.41,136.06,132.51,131.97,129.67,128.00,122.16,118.94.HRMS-EI(m/z):Calc.for C13H13NSi[M]+211.0817,found 211.0815.
P11:phenyl(1-(thiophen-2-yl)vinyl)silane
(原料为)
无色油状液体,收率:99%。1H NMR(500MHz,CDCl3)δ7.66-7.63(m,2H),7.46-7.38(m,3H),7.31-7.25(m,2H),7.23-7.21(m,1H),6.31(d,J=2.3Hz,1H),5.80(d,J=2.4Hz,1H),4.85(s,2H).
实施例2:Co-ICmPy催化的末端炔烃与二苯硅烷的马氏氢硅化反应:
惰性氛围下,向Schlenk管中加入配体(16.0mg,0.05mmol),Co(OAc)2(7.3mg,0.04mmol),炔烃(1.0mmol),Ph2SiH2(221mg,1.2mmol),THF(2.0mL),将得到的混合物在40℃下搅拌10小时。反应体系冷却至室温,浓缩,粗产物快速硅胶柱层析得到最终产物。
P12:diphenyl(1-phenylvinyl)silane
(原料为)
无色油状液体,收率:76%。1H NMR(500MHz,CDCl3)δ7.56(d,J=7.9,1.3Hz,4H),7.41-7.31(m,8H),7.27-7.19(m,3H),6.28(d,J=2.5Hz,1H),5.69(d,J=2.4Hz,1H),5.39(s,1H).
P13:diphenyl(1-(m-tolyl)vinyl)silane
(原料为)
白色固体,收率:47%。1H NMR(500MHz,CDCl3)δ7.57(dd,J=7.8,1.4Hz,4H),7.42-7.33(m,6H),7.18-7.11(m,3H),7.05-7.01(m,1H),6.27(d,J=1.9Hz,1H),5.66(d,J=2.5Hz,1H),5.39(s,1H),2.29(s,3H).
P14:diphenyl(1-(p-tolyl)vinyl)silane
(原料为)
白色固体,收率:56%。1H NMR(500MHz,CDCl3)δ7.58(dd,J=7.8,1.4Hz,4H),7.42-7.34(m,6H),7.29-7.25(m,2H),7.08(d,J=8.0Hz,2H),6.29(dd,J=2.5,0.9Hz,1H),5.65(d,J=2.5Hz,1H),5.40(s,1H),2.31(s,3H).
P15:(1-(4-(tert-butyl)phenyl)vinyl)diphenylsilane
(原料为)
白色固体,收率:58%。1H NMR(500MHz,CDCl3)δ7.61(dd,J=7.8,1.3Hz,4H),7.41(dd,J=17.8,7.3Hz,7H),7.32(q,J=8.6Hz,4H),6.33(d,J=1.4Hz,1H),5.67(d,J=2.4Hz,1H),5.42(s,1H),1.32(s,9H).13C NMR(126MHz,CDCl3)δ150.25,145.43,139.97,135.97,133.46,131.51,129.90,128.18,126.49,125.48,34.62,31.45.HRMS-EI(m/z):Calc.for C24H26Si[M]+342.1804,found342.1826.
P16:diphenyl(1-(thiophen-3-yl)vinyl)silane
(原料为)
浅黄色固体,收率:53%。1H NMR(500MHz,CDCl3)δ7.60(dd,J=7.9,1.3Hz,4H),7.46-7.37(m,6H),7.27-7.21(m,2H),7.14(dd,J=2.8,1.4Hz,1H),6.36(d,J=2.0Hz,1H),5.65(d,J=2.5Hz,1H),5.40(s,1H).
实施例3:Co-ICmPy催化的内炔与苯硅烷的氢硅化反应:
惰性氛围下,向反应管中依次加入炔烃(1mmol),苯硅烷(1.5mmol),THF(1mL)和1mL已溶清的催化剂溶液(配体:19.3mg,0.06mmol;Co(OAc)2:8.9mg,0.05mmol;THF:10.0mL),并将得到的混合物在室温下搅拌3小时。30℃水浴下反应2h,反应体系冷却至室温,浓缩,粗产物快速硅胶柱层析得到最终产物。
P17:(E)-phenyl(1-phenylbut-1-en-1-yl)silane
(原料为)
无色油状液体,收率:68%(混合物总收率)。1H NMR(500MHz,CDCl3)δ7.55-7.51(m,2H),7.39-7.26(m,5H),7.21-7.15(m,1H),7.06-7.04(m,2H),6.26(t,J=7.1Hz,1H),4.69(s,2H),2.12(p,J=7.5Hz,2H),0.98(t,J=7.5Hz,3H);
P18:(E)-(1,2-diphenylvinyl)(phenyl)silane
(原料为)
无色油状液体,收率:86%。1H NMR(300MHz,CDCl3)δ7.59-7.55(m,2H),7.42-7.32(m,3H),7.27-7.23(m,3H),7.13-7.00(m,8H),4.81(s,2H);
实施例4:Co-ICmPy催化的内炔与二苯硅烷的氢硅化反应:
惰性氛围下,向Schlenk管中加入配体(16.0mg,0.05mmol),Co(OAc)2(7.3mg,0.04mmol),炔烃(1.0mmol),Ph2SiH2(221mg,1.2mmol)和THF(2.0mL),将得到的混合物在40℃下搅拌10小时。反应体系冷却至室温,浓缩,粗产物快速硅胶柱层析得到最终产物。
P19:(E)-diphenyl(1-phenylbut-1-en-1-yl)silane
(原料为)
白色固体,收率:77%。1H NMR(500MHz,CDCl3)δ7.53(dd,J=7.8,1.6Hz,3H),7.42-7.32(m,6H),7.25-7.21(m,2H),7.17-7.13(m,1H),7.02-6.98(m,2H),6.20(t,J=7.1Hz,1H),5.19(s,1H),2.12(p,J=7.3Hz,2H),0.97(t,J=7.5Hz,3H).
实施例5:Co-ICmPy催化的苯乙炔与苯硅烷的马氏氢硅化反应:
按照炔烃与PhSiH3反应的一般程序,进行5mmol规模的氢硅化反应。50mL Schlenk管配置磁力搅拌,依次加入苯乙炔(510mg,5mmol),PhSiH3(810mg,7.5mmol)和THF(2mL)。然后加入配置好100μL催化剂溶液(配体:38.5mg,0.12mmol;Co(OAc)2:17.7mg,0.1mmol;THF:10.0mL),在30℃下反应3h,苯乙炔完全转化,定量得到目标产物(GC收率99%,选择性95%),在此催化剂量下(0.02mol%)反应的TON可以达到4950。
对比例
现有技术在惰性氛围下,向Schlenk管中加入苯乙炔(0.5mmol),PhSiH3(0.5mmol),催化剂(0.085mol%),THF(1mL),最后加入活化剂NaBHEt3(0.255mol%),反应1h,原料基本完全转化,加成产物与的气相总收率86%,与的比例为84:16(Org.Lett.2018,20,6265-6269.)。
最后,还需要注意的是,以上列举的仅是本发明若干个具体实施例。显然,本发明不限于以上实施例,还可以有许多变形。凡是利用本发明说明书内容所作的等效结构或等效流程变换,或直接或间接运用在其它相关的技术领域,均同理包括在本发明的专利保护范围内。
Claims (4)
1.一种制备α-烯基硅烷类化合物的方法,其特征在于,所述方法为:
在惰性气体保护下,将炔烃、硅烷、钴盐、吡啶亚胺类双齿氮配体、反应溶剂混合,于30~60℃下反应1~10h,之后经后处理,得到α-烯基硅烷类化合物;
所述炔烃、硅烷、钴盐、吡啶亚胺类双齿氮配体的物质的量之比为1:1.2~1.5:0.0002~0.04:0.00025~0.05;
所述钴盐为CoX2,其中X为卤素、OAc、acac或OTf;
所述炔烃的结构式为其中R1、R2各自独立为芳基、杂芳基、烷基或氢;
所述硅烷的结构式为R15R16R17SiH,其中R15、R16、R17各自独立为氢、烷基、烷氧基或芳基;
所述吡啶亚胺类双齿氮配体的结构式为其中R18为氢、烷基、芳基、萘基或烷氧基,R19为烷基、芳基或萘基,R20、R21各自独立为氢或烷基;
其中,
所述芳基表示:杂芳基表示: Y为N、O或S,R3~R14各自独立为氢、卤素、烷基、烷氧基、氨基、羟基、氰基或芳基;
“烷基”表示C1~C6烷基;
“烷氧基”表示C1~C6烷氧基。
2.如权利要求1所述的制备α-烯基硅烷类化合物的方法,其特征在于,所述反应溶剂选自:四氢呋喃、乙醚、苯、甲苯、乙酸乙酯、二氯甲烷、乙腈、石油醚、正己烷或N,N-二甲基甲酰胺。
3.如权利要求1所述的制备α-烯基硅烷类化合物的方法,其特征在于,所述反应溶剂的体积用量以炔烃的物质的量计为2~5mL/mmol。
4.如权利要求1所述的制备α-烯基硅烷类化合物的方法,其特征在于,所述后处理的方法为:反应结束后,待反应液冷却至室温,浓缩,硅胶柱层析分离,以石油醚为洗脱剂,收集含目标化合物的洗脱液,蒸除溶剂并干燥,得到α-烯基硅烷类化合物。
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