CN111620762B - 一种端基炔烃氢芳基化制备二取代烯烃的方法 - Google Patents
一种端基炔烃氢芳基化制备二取代烯烃的方法 Download PDFInfo
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- 150000001345 alkine derivatives Chemical class 0.000 title claims abstract description 32
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 24
- 238000003430 hydroarylation reaction Methods 0.000 title claims abstract description 22
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 229950011260 betanaphthol Drugs 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 238000004440 column chromatography Methods 0.000 claims description 9
- 239000003480 eluent Substances 0.000 claims description 9
- -1 aryl alkyne Chemical class 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 5
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical group ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- PYLWMHQQBFSUBP-UHFFFAOYSA-N monofluorobenzene Chemical compound FC1=CC=CC=C1 PYLWMHQQBFSUBP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 description 17
- 239000007788 liquid Substances 0.000 description 7
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 244000089409 Erythrina poeppigiana Species 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 235000009776 Rathbunia alamosensis Nutrition 0.000 description 2
- 229910004161 SiNa Inorganic materials 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- USCSRAJGJYMJFZ-UHFFFAOYSA-N 3-methyl-1-butyne Chemical compound CC(C)C#C USCSRAJGJYMJFZ-UHFFFAOYSA-N 0.000 description 1
- ZUKOCGMVJUXIJA-UHFFFAOYSA-N 6-chlorohex-1-yne Chemical compound ClCCCCC#C ZUKOCGMVJUXIJA-UHFFFAOYSA-N 0.000 description 1
- QJDUJHHCYRRDPF-UHFFFAOYSA-N 7-[tert-butyl(dimethyl)silyl]oxynaphthalen-2-ol Chemical compound C1=CC(O)=CC2=CC(O[Si](C)(C)C(C)(C)C)=CC=C21 QJDUJHHCYRRDPF-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000010485 C−C bond formation reaction Methods 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003460 anti-nuclear Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- ZVDBUOGYYYNMQI-UHFFFAOYSA-N dodec-1-yne Chemical compound CCCCCCCCCCC#C ZVDBUOGYYYNMQI-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- ZVYKVZXVRBCBTL-UHFFFAOYSA-K methylsulfanylmethane;trichlorogold Chemical compound CSC.Cl[Au](Cl)Cl ZVYKVZXVRBCBTL-UHFFFAOYSA-K 0.000 description 1
- 238000009206 nuclear medicine Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- NUZBJLXXTAOBPH-UHFFFAOYSA-N tert-butyl-but-3-ynoxy-dimethylsilane Chemical compound CC(C)(C)[Si](C)(C)OCCC#C NUZBJLXXTAOBPH-UHFFFAOYSA-N 0.000 description 1
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
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- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
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Abstract
本发明公开了一种端基炔烃氢芳基化制备二取代烯烃的方法,包括如下步骤:将端基炔烃、2‑萘酚、催化剂L1AuCl、NaBARF、
Description
技术领域
本发明属于有机合成技术领域,具体涉及一种端基炔烃氢芳基化制备二取代烯烃的方法。
背景技术
端基炔烃直接氢芳基化是制备二取代烯烃最有效的方法,现有技术中2-萘酚与端基炔烃制备二取代烯烃的反应均需要强酸或强路易斯酸以及高温(大于120℃)或微波等剧烈的反应条件,而且目前文献报道的合成方法反应仅局限于芳基取代炔烃,脂肪炔烃没有报道,例如文献:A)ASimple and Efficient Synthesis of 2,3-DiarylnaphthofuransUsing Sequential Hydroarylation/Heck Oxyarylation,Org.Lett.,2013,15,2190-2193;B)Hydroarylation of alkynes and alkenes through alumina-sulfuric acidcatalyzed regioselective C-C bond formation.Tetrahedron Lett.2019,60,1091-1095;C)Gallium(III)Chloride Catalyzed Hydroarylation of Arylacetylenes withNaphthols and Phenols:A Facile Synthesis of Vinylarenes.Synthesis 2009,2009,1301-1304(参见下面反应方程式),上述三篇文献ABC都需要高温条件且只耐受芳香炔烃,A需要微波操作,B需要当量的CaCl3,C需要浓硫酸。因此,研究一种温和条件下通过端基炔烃的直接氢芳基化来制备二取代烯烃的方法具有积极的意义。
现有技术文献ABC的反应方程式如下:
发明内容
为克服上述缺陷,本发明的目的在于提供一种温和条件下通过端基炔烃氢芳基化制备二取代烯烃的方法。
为实现上述目的,本发明采用如下技术方案:
一种端基炔烃氢芳基化制备二取代烯烃的方法,包括如下步骤:
所述端基炔烃为芳基炔烃或者脂肪炔烃;
优选地,所述的2-萘酚、端基炔烃、催化剂L1AuCl、NaBARF摩尔用量比为0.2mmol:0.28-0.32mmol:0.0016-0.0024mmol:0.008-0.012mmol。
优选地,所述的2-萘酚与溶剂用量比为0.2mmol:2-3mL。
优选地,所述的溶剂为DCE、二氯甲烷、氟苯、三氟甲苯或者THF。
优选地,所述的纯化为柱层析纯化,洗脱液为正己烷和乙酸乙酯,体积比为8-12:1。
本发明端基炔烃氢芳基化制备二取代烯烃的方法,反应方程式如下:
本发明的积极有益效果:
1.本发明端基炔烃氢芳基化制备二取代烯烃的方法,15-25℃条件下,空气气氛条件下就可实现,反应条件温和,产物收率高达95%,产物收率高,纯度大于95%,纯度高;端基炔烃可耐受诸多官能团,除了芳基之外,还包括脂肪烃基、氯、氟、OBn、OTBS等各类官能图,反应的普适性好。
具体实施方式
下面结合一些具体实施方式,对本发明进一步说明。
实施例1
一种端基炔烃氢芳基化制备二取代烯烃的方法,包括如下步骤:
将0.3mmol苯乙炔、0.2mmol 2-萘酚、0.002mmol催化剂L1AuCl、0.01mmol NaBARF、50mgMS和2mL DCE混合于反应瓶中,在20℃条件下搅拌反应2h,反应结束后,减压浓缩,柱层析纯化,洗脱液为正己烷和乙酸乙酯,体积比为10:1,得到二取代烯烃无色油状液体,收率92%,纯度大于95%,1H NMR(500MHz,CDCl3)δ7.85–7.75(m,2H),7.55–7.49(m,1H),7.41–7.34(m,2H),7.34–7.27(m,6H),6.34(d,J=1.3Hz,1H),5.62(s,1H),5.53(d,J=1.3Hz,1H).13C NMR(126MHz,CDCl3)δ150.42,142.55,138.76,132.79,129.66,128.95,128.76,128.58,128.06,126.56,126.33,124.91,123.34,120.06,118.97,117.35。
L1AuCl催化剂通过文献(Ageneral ligand design for goldcatalysis allowing ligand-directed anti-nucleophilic attack of alkynes.NatureCommunications,2014,5,3470.)报道的方法合成:将膦配体L1与二甲硫醚氯化金以摩尔比1:1的比例在二氯甲烷中搅拌0.5h,然后旋干,先用二氯甲烷溶解,再用正己烷重结晶,即得到目标催化剂L1AuCl。
实施例2-7采用同样的催化剂,以下不重述。
实施例2
一种端基炔烃氢芳基化制备二取代烯烃的方法,包括如下步骤:
将0.28mmol 1-十二炔、0.2mmol 2-萘酚、0.002mmol催化剂L1AuCl、0.012mmolNaBARF、52mg MS和3mL DCE混合于反应瓶中,在20℃条件下搅拌反应2h,反应结束后,减压浓缩,柱层析纯化,洗脱液为正己烷和乙酸乙酯,体积比为10:1,得到二取代烯烃无色油状液体,收率87%,纯度大于95%,1H NMR(400MHz,CDCl3)δ7.78(dd,J=8.2,1.3Hz,1H),7.75–7.64(m,2H),7.49–7.42(m,1H),7.33(ddd,J=8.0,6.7,1.2Hz,1H),7.21(d,J=8.8Hz,1H),5.71(q,J=1.6Hz,1H),5.66(s,1H),5.27(d,J=2.0Hz,1H),2.46(dtd,J=30.3,15.2,7.8Hz,2H),1.48(m 2H),1.29(m,14H),0.88(t,J=6.9Hz,3H).13C NMR(101MHz,CDCl3)δ149.15,145.48,131.96,128.83,128.80,128.17,126.29,124.27,123.13,121.87,118.30,118.30,37.82,31.87,29.58,29.55,29.43,29.28,28.29,22.66,14.10.HRMS m/z(ESI)Calcd for C22H30ONa[M+Na],333.2189,found333.2191。
实施例3
一种端基炔烃氢芳基化制备二取代烯烃的方法,包括如下步骤:
将0.3mmol 3-甲基-1-丁炔、0.2mmol 2-萘酚、0.0024mmol催化剂L1AuCl、0.01mmol NaBARF、52mgMS和3mL二氯甲烷混合于反应瓶中,在25℃条件下搅拌反应2h,反应结束后,减压浓缩,柱层析纯化,洗脱液为正己烷和乙酸乙酯,体积比为10:1,得到二取代烯烃无色油状液体,收率76%,纯度大于95%,1H NMR(500MHz,CDCl3)δ7.81–7.73(m,1H),7.70(dd,J=8.5,1.6Hz,2H),7.44(ddd,J=8.4,6.7,1.4Hz,1H),7.33(ddd,J=8.0,6.8,1.2Hz,1H),7.20(d,J=8.8Hz,1H),5.72–5.66(m,2H),5.34(d,J=2.1Hz,1H),2.44(ddd,J=14.5,5.1,1.5Hz,1H),2.32(dd,J=14.4,8.4Hz,1H),1.76–1.64(m,1H),1.02(d,J=6.6Hz,3H),0.90(d,J=6.6Hz,3H).13C NMR(126MHz,CDCl3)δ149.24,144.22,132.01,128.94,128.91,128.24,126.32,124.33,123.17,121.96,119.49,117.19,47.29,26.45,23.30,22.46.HRMS m/z(ESI)Calcd for C15H16ONa[M+Na],235.1093,found235.1094。
实施例4
一种端基炔烃氢芳基化制备二取代烯烃的方法,包括如下步骤:
将0.32mmol环己乙炔、0.2mmol 2-萘酚、0.002mmol催化剂L1AuCl、0.008mmolNaBARF、50mg MS和2mL DCE混合于反应瓶中,在20℃条件下搅拌反应4h,反应结束后,减压浓缩,柱层析纯化,洗脱液为正己烷和乙酸乙酯,体积比为10:1,得到二取代烯烃无色油状液体,收率95%,纯度大于95%,1H NMR(500MHz,CDCl3)δ7.78(dd,J=8.2,1.3Hz,1H),7.71(d,J=8.8Hz,1H),7.61(d,J=8.4Hz,1H),7.43(ddd,J=8.3,6.8,1.4Hz,1H),7.33(ddd,J=8.1,6.8,1.2Hz,1H),7.21(d,J=8.9Hz,1H),5.69(t,J=1.5Hz,1H),5.61(s,1H),5.26(d,J=1.6Hz,1H),2.28(ddd,J=11.6,8.1,3.2Hz,1H),2.12–2.03(m,1H),1.89–1.80(m,2H),1.72–1.64(m,2H),1.54–1.46(m,1H),1.30(dtd,J=12.7,9.4,2.6Hz,1H),1.22–1.08(m,3H).13C NMR(126MHz,CDCl3)δ150.56,149.45,132.34,128.90,128.76,128.19,126.24,124.52,123.10,122.27,117.04,116.40,44.77,33.48,31.21,26.69,26.46,26.22.HRMS m/z(ESI)Calcd for C18H20ONa[M+Na],275.1406,found275.1411。
实施例5
一种端基炔烃氢芳基化制备二取代烯烃的方法,包括如下步骤:
将0.28mmol 6-氯己炔、0.2mmol 2-萘酚、0.0016mmol催化剂L1AuCl、0.01mmolNaBARF、48mg MS和2.5mL DCE混合于反应瓶中,在20℃条件下搅拌反应3h,反应结束后,减压浓缩,柱层析纯化,洗脱液为正己烷和乙酸乙酯,体积比为10/1,得到二取代烯烃无色油状液体,收率72%,纯度大于95%,1H NMR(500MHz,CDCl3)δ7.78(dt,1H,J=8.2,0.8Hz),7.72(d,1H,J=8.8Hz),7.66(dq,1H,J=8.4,0.9Hz),7.44(ddd,1H,J=8.4,6.8,1.4Hz),7.34(ddd,1H,J=8.1,6.8,1.2Hz),7.21(d,1H,J=8.9Hz),5.74(q,1H,J=1.6Hz),5.61(s,1H),5.30(dd,1H,J=1.8,0.9Hz),3.50(td,2H,J=6.6,1.0Hz),2.59–2.44(m,2H),1.85–1.74(m,2H),1.68–1.61(m,2H).13C NMR(126MHz,CDCl3)δ149.2,144.7,132.0,129.0,128.9,128.3,126.5,124.2,123.3,121.5,118.8,117.2,44.7,36.9,32.4,25.5.HRMS m/z(ESI)Calcd for C16H17OClNa[M+Na],283.0860,found283.0855。
实施例6
一种端基炔烃氢芳基化制备二取代烯烃的方法,包括如下步骤:
将0.3mmol 4-(叔丁基二甲硅氧基)-1-丁炔、0.2mmol 2-萘酚、0.0022mmol催化剂L1AuCl、0.01mmol NaBARF、50mgMS和2.4mL THF混合于反应瓶中,在15℃条件下搅拌反应4h,反应结束后,减压浓缩,柱层析纯化,洗脱液为正己烷和乙酸乙酯,体积比为10:1,得到二取代烯烃无色油状液体,收率77%,纯度大于95%,1H NMR(400MHz,CDCl3)δ7.80–7.74(m,1H),7.71(dd,2H,J=9.0,2.2Hz),7.42(ddd,1H,J=8.3,6.8,1.3Hz),7.35–7.25(m,2H),7.20(d,1H,J=8.8Hz),5.69(dt,1H,J=2.2,1.1Hz),5.31(d,1H,J=2.2Hz),3.81–3.74(m,1H),3.68–3.59(m,1H),2.79(td,1H,J=12.2,11.3,4.9Hz),2.57(d,1H,J=13.5Hz),0.97(s,9H),0.14(d,6H,J=6.0Hz).13C NMR(126MHz,CDCl3)δ151.3,140.6,132.6,128.8,128.6,128.1,126.2,124.0,122.8,122.2,120.5,118.4,60.5,41.1,25.9,18.3,-5.2,-5.4.HRMS m/z(ESI)Calcd for C20H28O2SiNa[M+Na],351.1751,found 351.1755。
实施例7
一种端基炔烃氢芳基化制备二取代烯烃的方法,包括如下步骤:
将0.3mmol苯乙炔、0.2mmol 7-叔丁基二甲基硅氧基-2-萘酚、0.002mmol催化剂L1AuCl、0.012mmol NaBARF、50mgMS和2mL DCE混合于反应瓶中,在15℃条件下搅拌反应3h,反应结束后,减压浓缩,柱层析纯化,洗脱液为正己烷和乙酸乙酯,体积比为10:1,得到二取代烯烃无色油状液体,收率90%,纯度大于95%,1H NMR(400MHz,CDCl3)δ7.90–7.71(m,1H),7.70–7.64(m,1H),7.40(ddd,J=7.1,4.6,4.2Hz,1H),7.31(t,J=3.4Hz,1H),7.16(t,J=8.1Hz,1H),6.98–6.89(m,1H),6.86–6.77(m,1H),6.41–6.20(m,1H),5.87–5.74(m,1H),5.60–5.43(m,1H),0.91(s,9H),0.03(s,3H),-0.03(s,3H).13C NMR(101MHz,CDCl3)δ154.18,150.94,143.04,138.97,133.94,129.48,129.35,128.75,128.55,126.41,124.60,119.35,118.81,118.63,115.02,112.71,25.68,18.23,-4.57,-4.84.HRMS m/z(ESI)Calcd for C24H28O2SiNa[M+Na],399.1751,found 399.1748。
Claims (6)
2.根据权利要求1所述的一种端基炔烃氢芳基化制备二取代烯烃的方法,其特征在于,所述的2-萘酚、端基炔烃、催化剂L1AuCl、NaBARF摩尔用量比为0.2mmol:0.28-0.32mmol:0.0016-0.0024mmol:0.008-0.012mmol。
4.根据权利要求1所述的一种端基炔烃氢芳基化制备二取代烯烃的方法,其特征在于,所述的2-萘酚与溶剂用量比为0.2mmol:2-3mL。
5.根据权利要求1或者4所述的一种端基炔烃氢芳基化制备二取代烯烃的方法,其特征在于,所述的溶剂为DCE、二氯甲烷、氟苯、三氟甲苯或者THF。
6.根据权利要求1所述的一种端基炔烃氢芳基化制备二取代烯烃的方法,其特征在于,所述的纯化为柱层析纯化,洗脱液为正己烷和乙酸乙酯,体积比为8-12:1。
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Non-Patent Citations (14)
Title |
---|
3D Nanoporous FeAl-KIT-5 with a cage type pore structure a highly efficient and stable catalyst for hydroarylation of styrene and arylacetylenes;Shaji Varghese;《Tetrahedron Letters》;20120117;第53卷;1485-1489 * |
A general ligand design for gold catalysis allowing ligand-directed anti-nucleophilic attack of alkynes;Yanzhao Wang;《NATURE COMMUNICATIONS》;20141231;第5卷;1-8 * |
A Simple and Efficient Synthesis of 2,3-Diarylnaphthofurans Using Sequential Hydroarylation Heck Oxyarylation;V. Kameshwara Rao;《ORGANIC LETTERS》;20130415;第15卷(第9期);2190-2193 * |
Au(II)配合物催化剂室温高效催化炔烃水合反应;吴功德;《高等学校化学学报》;20151231;第36卷(第12期);2461-2467 * |
Bifunctional phosphine ligand-enabled gold-catalyzed direct cycloisomerization of alkynyl ketones to 2,5-disubstituted furans;Hu, Xiaojun;《Chemical Communications》;20200610;第56卷(第53期);7297-7300 * |
Casiraghi, G..Selective o-Vinylation of Phenols * |
Electrophilic alkenylation of aromatics with phenylacetylene over zeolite HSZ-360;Giovanni Sartori;《Tetrahedron Letters》;19951231;第36卷(第50期);9177-9180 * |
Gallium(III) Chloride Catalyzed Hydroarylation of Arylacetylenes with Naphthols and Phenols A Facile Synthesis of Vinylarenes;Jhillu S.Yadav;《SYNTHESIS》;20091231(第8期);1301-1304 * |
Highly Efficient One-Pot Synthesis of 2,4-Disubstituted Thiazoles Using Au(I) Catalyzed Oxidation System at Room Temperature;Wu, Gongde;《Catalysts》;20161231;第6卷(第8期);1-9 * |
Hydroarylation of alkynes and alkenes through alumina-sulfuric acid catalyzed regioselective C-C bond formation;Amit Pramanik;《Tetrahedron Letters》;20190304;第60卷;1091-1095 * |
Iodine-Mediated, Microwave-Assisted Synthesis of 1-Arylnaphthofurans via Cyclization of 1-(1′-Arylvinyl)-2-naphthols;V. Kameshwara Rao;《Synthesis》;20150918;第47卷;3990-3996 * |
Ligand-Accelerated Gold-Catalyzed Addition of in Situ Generated Hydrazoic Acid to Alkynes under Neat Conditions;Li, Xiaoqing;《Organic Letters》;20171231;第19卷(第14期);3687-3690 * |
Moskalev-Hydroarylation of Alkynes with Phenols in the Presence of Gallium Complexes of a Labile N-Ligand: Synthesis of Chromenes;Mikhail V. Moskalev;《European J Organic Chem》;20151231;5781-5788 * |
Synthesis of 2-(1-Phenylethenyl)-phenols.《Synthesis》.1977,(第2期),122-4. * |
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