CN114805268B - 可见光介导的环戊[b]苯并呋喃衍生物的合成方法 - Google Patents
可见光介导的环戊[b]苯并呋喃衍生物的合成方法 Download PDFInfo
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- CN114805268B CN114805268B CN202210457693.1A CN202210457693A CN114805268B CN 114805268 B CN114805268 B CN 114805268B CN 202210457693 A CN202210457693 A CN 202210457693A CN 114805268 B CN114805268 B CN 114805268B
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- HYGDHSYCSJKRFX-UHFFFAOYSA-N 1h-cyclopenta[b][1]benzofuran Chemical class O1C2=CC=CC=C2C2=C1C=CC2 HYGDHSYCSJKRFX-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 230000001404 mediated effect Effects 0.000 title claims abstract description 14
- 238000001308 synthesis method Methods 0.000 title description 2
- -1 bromomalonic acid diester Chemical class 0.000 claims abstract description 46
- 239000002904 solvent Substances 0.000 claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000005286 illumination Methods 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 52
- 229910052786 argon Inorganic materials 0.000 claims description 26
- 239000003504 photosensitizing agent Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000003107 substituted aryl group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 150000001907 coumarones Chemical class 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 24
- 238000003786 synthesis reaction Methods 0.000 abstract description 24
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 69
- 238000005481 NMR spectroscopy Methods 0.000 description 58
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 52
- 239000000047 product Substances 0.000 description 47
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- FNJVDWXUKLTFFL-UHFFFAOYSA-N diethyl 2-bromopropanedioate Chemical compound CCOC(=O)C(Br)C(=O)OCC FNJVDWXUKLTFFL-UHFFFAOYSA-N 0.000 description 20
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- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 12
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 7
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- MZFXVNGQPJIXMA-UHFFFAOYSA-N 1-bromo-4-[2-(2-ethenoxyphenyl)ethynyl]benzene Chemical compound BrC1=CC=C(C=C1)C#CC1=C(C=CC=C1)OC=C MZFXVNGQPJIXMA-UHFFFAOYSA-N 0.000 description 1
- MJQSNVKKCRDDKO-UHFFFAOYSA-N 1-chloro-4-[2-(2-ethenoxyphenyl)ethynyl]benzene Chemical compound C=COC1=CC=CC=C1C#CC2=CC=C(C=C2)Cl MJQSNVKKCRDDKO-UHFFFAOYSA-N 0.000 description 1
- PIWYQZVEKVVYLS-UHFFFAOYSA-N 1-ethenoxy-2-[2-(2-fluorophenyl)ethynyl]benzene Chemical compound FC1=C(C=CC=C1)C#CC1=C(C=CC=C1)OC=C PIWYQZVEKVVYLS-UHFFFAOYSA-N 0.000 description 1
- SPSNAIWHXNSTJO-UHFFFAOYSA-N 1-ethenoxy-2-[2-(3-fluorophenyl)ethynyl]benzene Chemical compound C=COC(C=CC=C1)=C1C#CC1=CC(F)=CC=C1 SPSNAIWHXNSTJO-UHFFFAOYSA-N 0.000 description 1
- LSERWONWFOJKSI-UHFFFAOYSA-N 1-ethenoxy-2-[2-(4-fluorophenyl)ethynyl]benzene Chemical compound C=COC1=CC=CC=C1C#CC2=CC=C(C=C2)F LSERWONWFOJKSI-UHFFFAOYSA-N 0.000 description 1
- PXYKYRCJMYDQQW-UHFFFAOYSA-N 1-ethenoxy-2-[2-(4-methylphenyl)ethynyl]benzene Chemical compound C1(=CC=C(C=C1)C#CC1=C(C=CC=C1)OC=C)C PXYKYRCJMYDQQW-UHFFFAOYSA-N 0.000 description 1
- ISIALCKBVKAXRD-UHFFFAOYSA-N 1-ethenoxy-2-iodobenzene Chemical compound IC1=CC=CC=C1OC=C ISIALCKBVKAXRD-UHFFFAOYSA-N 0.000 description 1
- VBZOUUJVGADJBK-UHFFFAOYSA-N 2-bromopropanedioic acid Chemical compound OC(=O)C(Br)C(O)=O VBZOUUJVGADJBK-UHFFFAOYSA-N 0.000 description 1
- PWTAKRRIAJPVET-UHFFFAOYSA-N 2-ethenoxy-1-(2-phenylethynyl)naphthalene Chemical compound C=COC(C=CC1=CC=CC=C11)=C1C#CC1=CC=CC=C1 PWTAKRRIAJPVET-UHFFFAOYSA-N 0.000 description 1
- QVNXCIHXGPKSRO-UHFFFAOYSA-N 2-ethenoxy-4-fluoro-1-(2-phenylethynyl)benzene Chemical compound C=COC(C=C(C=C1)F)=C1C#CC1=CC=CC=C1 QVNXCIHXGPKSRO-UHFFFAOYSA-N 0.000 description 1
- LZSDQLUEGYXDCW-UHFFFAOYSA-N 2-ethynylbenzonitrile Chemical compound C#CC1=CC=CC=C1C#N LZSDQLUEGYXDCW-UHFFFAOYSA-N 0.000 description 1
- XVDVSWBNCGYPSE-UHFFFAOYSA-N 3-[2-(2-ethenoxyphenyl)ethynyl]thiophene Chemical compound C=COC(C=CC=C1)=C1C#CC1=CSC=C1 XVDVSWBNCGYPSE-UHFFFAOYSA-N 0.000 description 1
- 125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 description 1
- YPDDLOMEMFYKGI-UHFFFAOYSA-N 3h-thiophene-2,2-dicarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CC=CS1 YPDDLOMEMFYKGI-UHFFFAOYSA-N 0.000 description 1
- ABIZXRMSKZWVLM-UHFFFAOYSA-N 4-[2-(2-ethenoxyphenyl)ethynyl]benzonitrile Chemical compound C(=C)OC1=C(C=CC=C1)C#CC1=CC=C(C#N)C=C1 ABIZXRMSKZWVLM-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
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- QRVSDVDFJFKYKA-UHFFFAOYSA-N dipropan-2-yl propanedioate Chemical compound CC(C)OC(=O)CC(=O)OC(C)C QRVSDVDFJFKYKA-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- ACEONLNNWKIPTM-UHFFFAOYSA-N methyl 2-bromopropanoate Chemical compound COC(=O)C(C)Br ACEONLNNWKIPTM-UHFFFAOYSA-N 0.000 description 1
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- CUQOHAYJWVTKDE-UHFFFAOYSA-N potassium;butan-1-olate Chemical compound [K+].CCCC[O-] CUQOHAYJWVTKDE-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/93—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems condensed with a ring other than six-membered
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
- C07D333/78—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems condensed with rings other than six-membered or with ring systems containing such rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
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Abstract
本发明属于化合物合成技术领域,具体涉及可见光介导的环戊[b]苯并呋喃衍生物的合成方法。该方法是将式1所示的1,6‑烯炔和式2所示的溴丙二酸二酯加入溶剂中,在室温和惰性气氛下,于可见光条件下发生5‑exo‑dig环化反应,再通过1,5氢迁移后,发生5‑endo‑trig环化反应,合成式3所示的环戊[b]苯并呋喃衍生物。本发明中反应操作简单,不需要过多处理,反应结束后即可直接进行分离。在本发明中能以可观的产率获得相应产物,且整个反应在光照条件下进行,不需要加热,绿色环保。
Description
技术领域
本发明属于化合物制备技术领域,具体涉及可见光介导的环戊[b]苯并呋喃衍生物的合成方法。
背景技术
在2017年,李金恒课题组报道了Ag2CO3和Cu(MeCN)4PF6作为催化剂,以TBHP为氧化剂,利用1,6-烯炔和2-溴丙酸甲酯作为底物合成一系列环戊[b]苯并呋喃衍生物的方法,该方法虽然产率较好,但是需采用加热条件,反应条件剧烈(Chem.Commun.2016,52,3328–3331)。
尽管环戊[b]苯并呋喃的合成取得了显著的进展,但大多数传统方法都面临着恶劣的条件、官能团耐受性有限和/或催化系统的成本。此外,环戊[b]苯并呋喃支架的组装仍然是一个巨大的挑战。因此,对环戊[b]苯并呋喃衍生物开发温和和有效的路线,特别是无金属策略是可取的。
综上所述,在目前从简单易得的底物直接合成环戊[b]苯并呋喃的报道中,仍然存在着底物范围有限、反应条件剧烈等问题。
发明内容
本发明开发了一种可见光介导的串联自由基环化1,6-烯炔与溴丙二酸二酯合成环戊[b]苯并呋喃衍生物的方法。该方法为具有广泛官能团耐受性,高效且环境友好,产率适中至良好。
本发明提供一种可见光介导的环戊[b]苯并呋喃衍生物的合成方法,包括以下内容:
将式1所示的1,6-烯炔和式2所示的溴丙二酸二酯加入溶剂中,在室温和惰性气氛下,于可见光条件下发生5-exo-dig环化反应,再通过1,5氢迁移后,发生5-endo-trig环化反应,合成式3所示的环戊[b]苯并呋喃衍生物。
合成路线如下:
其中:X为O,S;R1选自氢、甲基、甲氧基、卤素或稠环;R2选自烷基、杂芳基或取代芳基,所述取代芳基为氢、氰基、卤素、苯基、甲氧基、直链烷基取代芳基;R3选自直链烷基。hv表示可见光,inert gas表示惰性气氛,solvent表示溶剂,temp表示室温。
所述溶剂为DMF。所述惰性气氛为氩气。所述光照条件为紫光、白炽灯光或氙灯光。优选地,所述可见光的波长为405nm。
其中,式1所示的1,6-烯炔和式2所示的溴丙二酸二酯的摩尔比为1:1.5。
所述溶剂的加入量均为式1所示的1,6-烯炔的1000mol%。
上述反应中还可以加入光敏剂,所述光敏剂为金属配合物或有机光敏剂,具体可以为fac-Ir(ppy)3。所述光敏剂的加入量为式1所示的1,6-烯炔的1mol%。
相比现有技术,本发明的有益效果在于:
本发明方法中,溴丙二酸二酯在可见光光照的作用下形成自由基,随后与1,6-烯炔反应形成烯基自由基,可见光光照条件下发生5-exo-dig环化反应,再通过1,5氢迁移后,发生5-endo-trig环化反应,合成式3所示的环戊[b]苯并呋喃衍生物。
目前还没有以溴丙二酸二酯为原料、通过自由基反应合成环戊[b]苯并呋喃类化合物的报道,而本发明在可见光光照条件下,使得1,6-烯炔可以与溴丙二酸二酯反应,得到环戊[b]苯并呋喃衍生物。
本发明中反应操作简单,不需要过多处理,反应结束后可直接进行分离。在本发明中能以可观的产率获得相应产物,且整个反应在光照条件下进行,不需要加热,绿色环保。
附图说明
图1为本发明实施例一中1-苯基-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的核磁共振氢谱图(上图)和碳谱图(下图)。
图2为本发明实施例二中1-(4-甲基苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的核磁共振氢谱图。
图3为本发明实施例三中1-(4-乙基苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的核磁共振氢谱图。
图4为本发明实施例四中1-(4-甲氧基苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的核磁共振氢谱图。
图5为本发明实施例七中-1-(4-氯苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的核磁共振氢谱图。
图6为本发明中实施例二十五中1-(苯乙炔基)-2-(乙烯基氧基)苯的核磁共振氢谱图(上图)和碳谱图(下图)。
图7为本发明中实施例二十五中1-((4-乙基苯基)乙炔基)-2-(乙烯基氧基)苯的核磁共振氢谱图(上图)和碳谱图(下图)。
图8为本发明中实施例二十五中4-氯-2-(苯乙炔基)-1-(乙烯基氧基)苯的核磁共振氢谱图(上图)和碳谱图(下图)。
图9为本发明中实施例二十五中1-((4-溴苯基)乙炔基)-2-(乙烯基氧基)苯的核磁共振氢谱图(上图)和碳谱图(下图)。
图10为本发明实施例二十五中4-((2-(乙烯基氧基)苯基)乙炔基)苄腈核磁共振氢谱图(上图)和碳谱图(下图)。
图11本发明实施例二十五中1-((4-甲氧基苯基)乙炔基)-2-(乙烯基氧基)苯的核磁共振氢谱图(上图)和碳谱图(下图)。
图12本发明实施例二十五中(2-(苯基乙炔基)苯基)(乙烯基)硫烷的核磁共振氢谱图(上图)和碳谱图(下图)。
图13本发明实施例二十五中4-甲氧基-2-(苯乙炔基)-1-(乙烯基氧基)苯的核磁共振氢谱图(上图)和碳谱图(下图)。
具体实施方式
下面通过具体实施方式对本发明进行更加详细的说明,以便于对本发明技术方案的理解,但并不用于对本发明保护范围的限制。
实施例一1-苯基-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的合成
向配备有搅拌棒的10mL Schlenk管中加入1-(苯乙炔基)-2-(乙烯基氧基)苯(0.2mmol)、溴丙二酸二乙酯(0.3mmol)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物1-苯基-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯,产率为74%。
产物的核磁数据和高分辨质谱:1H NMR(300MHz,CDCl3)δ7.51(d,J=8.2Hz,1H),7.32–7.20(m,6H),7.20–7.07(m,2H),5.44(d,J=0.9Hz,1H),4.47–4.22(m,2H),4.09–4.03(m,1H),3.83–3.65(m,1H),3.51–3.31(m,2H),1.34(t,J=7.1Hz,3H),0.89(t,J=7.1Hz,3H).13C NMR(75MHz,CDCl3)δ171.2,168.8,160.5,158.3,138.1,129.2,128.0,127.5,125.3,123.2,122.8,121.1,119.3,111.8,70.0,62.0,61.5,48.9,34.0,14.0,13.4.HRMS(ESI)m/z:[M+Na]+Calcd for 401.1359C23H22O5Na,found 401.1351.
实施例二1-(4-甲基苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的合成
向配备有搅拌棒的10mL Schlenk管中加入1-(对甲苯乙炔基)-2-(乙烯基氧基)苯(0.2mmol)、溴丙二酸二乙酯(0.3mmol)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物1-(4-甲基苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯,产率为68%。
产物的核磁数据和高分辨质谱:1H NMR(300MHz,CDCl3)δ7.46(d,J=8.2Hz,1H),7.24–7.14(m,1H),7.13–6.98(m,6H),5.36(d,J=1.3Hz,1H),4.45–4.16(m,2H),4.08–3.92(m,1H),3.80–3.64(m,1H),3.49–3.27(m,2H),2.29(s,3H),1.29(t,J=7.1Hz,3H),0.87(t,J=7.2Hz,3H).13C NMR(75MHz,CDCl3)δ171.2,168.8,160.4,158.2,137.0,134.9,129.0,128.6,125.4,123.2,122.7,121.2,119.3,111.8,70.0,62.0,61.4,48.5,33.8,21.0,14.0,13.4.HRMS(ESI)m/z:[M+Na]+Calcd for 415.1516C24H24O5Na,found 415.1516.
实施例三1-(4-乙基苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的合成
向配备有搅拌棒的10mL Schlenk管中加入1-((4-乙基苯基)乙炔基)-2-(乙烯基氧基)苯(0.2mmol)、溴丙二酸二乙酯(0.3mmol)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物1-(4-乙基苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯,产率为63%。
产物的核磁数据和高分辨质谱:1H NMR(300MHz,CDCl3)δ7.46(d,J=8.2Hz,1H),7.23–7.01(m,7H),5.37(s,1H),4.40–4.16(m,2H),4.09–3.90(m,1H),3.78–3.62(m,1H),3.49–3.25(m,2H),2.59(q,J=7.6Hz,2H),1.29(t,J=7.1Hz,3H),1.18(t,J=7.6Hz,3H),0.83(t,J=7.1Hz,3H).13C NMR(75MHz,CDCl3)δ171.2,168.9,160.5,158.3,143.5,135.2,129.1,127.4,125.4,123.2,122.8,121.2,119.4,111.8,62.0,61.4,48.6,33.9,28.5,15.7,14.0,13.4.HRMS(ESI)m/z:[M+Na]+Calcd for 429.1672C25H26O5Na,found 429.1673.
实施例四1-(4-甲氧基苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的合成
向配备有搅拌棒的10mL Schlenk管中加入1-((4-甲氧基苯基)乙炔基)-2-(乙烯基氧基)苯(0.2mmol)、溴丙二酸二乙酯(0.3mmol)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物1-(4-甲氧基苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯,产率为50%。
产物的核磁数据和高分辨质谱:1H NMR(300MHz,CDCl3)δ7.50(d,J=8.2Hz,1H),7.29–7.05(m,5H),6.81(d,J=8.7Hz,2H),5.39(s,1H),4.45–4.21(m,2H),4.10–3.96(m,1H),3.89–3.69(m,4H),3.58–3.32(m,2H),1.34(t,J=7.1Hz,3H),0.94(t,J=7.1Hz,3H).13C NMR(75MHz,CDCl3)δ171.2,168.9,160.5,158.9,158.2,130.2,130.0,125.4,123.2,122.8,121.2,120.0,113.3,111.8,70.0,62.0,61.5,55.2,48.2,33.8,14.0,13.5.HRMS(ESI)m/z:[M+Na]+Calcd for 431.1465C24H24O6Na,found 431.1466.
实施例五1-([1,1'-联苯]-4-基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的合成
向配备有搅拌棒的10mL Schlenk管中加入4-((2-(乙烯基氧基)苯基)乙炔基)-1,1'-联苯(0.2mmol)、溴丙二酸二乙酯(0.3mmol)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物1-([1,1'-联苯]-4-基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯,产率为58%。
产物的核磁数据和高分辨质谱:1H NMR(300MHz,CDCl3)δ7.60–7.52(m,2H),7.52–7.38(m,5H),7.37–7.27(m,3H),7.25–7.15(m,1H),7.15–7.05(m,2H),5.45(s,1H),4.44–4.20(m,2H),4.13–3.96(m,1H),3.80–3.63(m,1H),3.52–3.29(m,2H),1.31(t,J=7.1Hz,3H),0.84(t,J=7.1Hz,3H).13C NMR(75MHz,CDCl3)δ171.1,168.8,160.5,158.4,140.7,140.3,137.2,129.6,128.7,127.2,126.9,126.6,125.3,123.3,122.8,121.0,119.3,111.9,70.1,62.1,61.6,48.6,34.0,14.0,13.4.HRMS(ESI)m/z:[M+Na]+Calcd for477.1672C29H26O5Na,found 477.1673.
实施例六1-(4-氟苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的合成
向配备有搅拌棒的10mL Schlenk管中加入1-((4-氟苯基)乙炔基)-2-(乙烯基氧基)苯(0.2mmol)、溴丙二酸二乙酯(0.3mmol)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物1-(4-氟苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯,产率为67%。
产物的核磁数据和高分辨质谱:1H NMR(300MHz,CDCl3)δ7.47(d,J=8.2Hz,1H),7.25–7.14(m,3H),7.15–7.01(m,2H),6.93(t,J=8.7Hz,2H),5.38(s,1H),4.42–4.16(m,2H),1H NMR 4.05–3.91(m,1H),3.82–3.66(m,1H),3.51–3.28(m,2H),1.30(t,J=7.1Hz,3H),0.89(t,J=7.2Hz,3H).13C NMR(75MHz,CDCl3)δ171.0,168.7,162.2(d,1JC-F=245.9Hz),160.5,158.4,133.8(d,4JC-F=3.2Hz),130.8(d,3JC-F=8.1Hz),125.1,123.3,122.9,120.8,119.1,114.8(d,2JC-F=21.3Hz),111.9,69.9,62.1,61.5,48.1,33.9,14.0,13.5.HRMS(ESI)m/z:[M+Na]+Calcd for 419.1265C23H21O5FNa,found 419.1262.
实施例七1-(4-氯苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的合成
向配备有搅拌棒的10mL Schlenk管中加入1-((4-氯苯基)乙炔基)-2-(乙烯基氧基)苯(0.2mmol)、溴丙二酸二乙酯(0.3mmol)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物1-(4-氯苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯,产率为68%。
产物的核磁数据和高分辨质谱:1H NMR(300MHz,CDCl3)δ7.47(d,J=8.2Hz,1H),7.25–7.15(m,5H),7.15–6.99(m,2H),5.38(s,1H),4.43–4.16(m,2H),4.07–3.89(m,1H),3.84–3.66(m,1H),3.55–3.27(m,2H),1.30(t,J=7.1Hz,3H),0.89(t,J=7.2Hz,3H).13CNMR(75MHz,CDCl3)δ170.9,168.6,160.5,158.5,136.7,133.3,130.6,128.1,125.1,123.4,122.9,120.6,119.1,111.9,69.9,62.1,61.6,48.3,33.9,14.0,13.5.HRMS(ESI)m/z:[M+Na]+Calcd for 435.0970C23H21O5ClNa,found 435.0960.
实施例八1-(4-溴苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的合成
向配备有搅拌棒的10mL Schlenk管中加入-((4-溴苯基)乙炔基)-2-(乙烯基氧基)苯(0.2mmol)、溴丙二酸二乙酯(0.3mmol)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物1-(4-溴苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯,产率为56%。
产物的核磁数据和高分辨质谱:1H NMR(300MHz,CDCl3)δ7.47(d,J=8.2Hz,1H),7.37(d,J=8.4Hz,2H),7.25–7.17(m,1H),7.17–7.00(m,4H),5.36(s,1H),4.45–4.15(m,2H),4.09–3.89(m,1H),3.85–3.65(m,1H),3.56–3.28(m,2H),1.30(t,J=7.1Hz,3H),0.89(t,J=7.1Hz,3H).13C NMR(75MHz,CDCl3)δ170.9,168.6,160.5,158.5,137.2,131.1,130.9,125.1,123.4,122.9,121.5,120.5,119.1,111.9,69.8,62.1,61.6,48.3,33.9,14.0,13.5.HRMS(ESI)m/z:[M+Na]+Calcd for 479.0465C23H21O5BrNa,found 479.0471.
实施例九1-(4-氰基苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的合成
向配备有搅拌棒的10mL Schlenk管中加入4-((2-(乙烯基氧基)苯基)乙炔基)苄腈(0.2mmol)、溴丙二酸二乙酯(0.3mmol)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物1-(4-氰基苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯,产率为70%。
产物的核磁数据和高分辨质谱:1H NMR(300MHz,CDCl3)δ7.56(d,J=8.3Hz,2H),7.48(d,J=8.3Hz,1H),7.38(d,J=8.2Hz,2H),7.27–7.18(m,1H),7.12(t,J=7.5Hz,1H),7.00(d,J=7.5Hz,1H),5.45(s,1H),4.46–4.15(m,2H),4.10–3.91(m,1H),3.81–3.64(m,1H),3.50–3.30(m,2H),1.30(t,J=7.1Hz,3H),0.86(t,J=7.1Hz,3H).13C NMR(75MHz,CDCl3)δ170.7,168.4,160.5,158.8,144.0,131.8,130.1,124.8,123.6,123.1,119.8,118.9,118.7,112.1,111.4,69.9,62.4,61.7,48.8,34.0,14.0,13.5.HRMS(ESI)m/z:[M+Na]+Calcd for426.1312C24H21O5NNa,found 426.1311.
实施例十1-(2-氟苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的合成
向配备有搅拌棒的10mL Schlenk管中加入1-氟-2-((2-(乙烯基氧基)苯基)乙炔基)苯(0.2mmol)、溴丙二酸二乙酯(0.3mmol)、fac-Ir(ppy)3(1mol%)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物1-(2-氟苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯,产率为40%。
产物的核磁数据和高分辨质谱:1H NMR(300MHz,CDCl3)δ7.46(d,J=8.2Hz,1H),7.25–7.14(m,2H),7.14–6.99(m,3H),7.00–6.83(m,2H),5.77(s,1H),4.42–4.18(m,2H),4.19–4.04(m,1H),3.87–3.70(m,1H),3.53–3.26(m,2H),1.29(t,J=7.1Hz,3H),0.92(t,J=7.2Hz,3H).13C NMR(75MHz,CDCl3)δ170.7,168.5,161.1(d,1JC-F=248.6Hz),160.6,158.3,130.18,129.13(d,3JC-F=8.2Hz),125.6(d,2JC-F=14.1Hz),125.0,123.8(d,3JC-F=3.6Hz),123.4,122.9,120.6,119.1,115.1(d,2JC-F=22.4Hz),111.9,69.4,62.1,61.6,33.9,14.0,13.4.HRMS(ESI)m/z:[M+Na]+Calcd for 419.1265C23H21O5FNa,found419.1266.实施例十一1-(3-氟苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的合成
向配备有搅拌棒的10mL Schlenk管中加入1-((3-氟苯基)乙炔基)-2-(乙烯基氧基)苯(0.2mmol)、溴丙二酸二乙酯(0.3mmol)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物1-(3-氟苯基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯,产率为67%。
产物的核磁数据和高分辨质谱:1H NMR(300MHz,CDCl3)δ7.47(d,J=8.2Hz,1H),7.25–7.16(m,2H),7.14–7.06(m,2H),7.03–6.90(m,3H),5.39(s,1H),4.44–4.17(m,2H),4.06–3.92(m,1H),3.83–3.68(m,1H),3.54–3.29(m,2H),1.30(t,J=7.1Hz,3H),0.89(t,J=7.2Hz,3H).13C NMR(75MHz,CDCl3)δ170.9,168.5,162.6(d,1JC-F=245.7Hz),160.5,158.5,140.9(d,3JC-F=7.0Hz),129.4(d,3JC-F=8.2Hz),125.1,124.81(d,4JC-F=2.8Hz),123.4,122.9,120.6,119.2,116.2(d,2JC-F=21.7Hz),114.4(d,2JC-F=21.2Hz),111.9,69.9,62.2,61.6,48.6(d,4JC-F=1.7Hz),33.9,14.0,13.4.HRMS(ESI)m/z:[M+Na]+Calcdfor 419.1265C23H21O5FNa,found 419.1269.
实施例十二1-(噻吩-3-基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的合成
向配备有搅拌棒的10mL Schlenk管中加入3-((2-(乙烯基氧基)苯基)乙炔基)噻吩(0.2mmol)、溴丙二酸二乙酯(0.3mmol)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物1-(噻吩-3-基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯,产率为55%。
产物的核磁数据和高分辨质谱:1H NMR(300MHz,CDCl3)δ7.46(d,J=8.1Hz,1H),7.24–7.10(m,4H),7.06(d,J=2.3Hz,1H),6.95(dd,J=4.9,1.1Hz,1H),5.46(s,1H),4.45–4.15(m,2H),4.02–3.90(m,1H),3.87–3.76(m,1H),3.59–3.48(m,1H),3.43–3.29(m,1H),1.30(t,J=7.1Hz,3H),0.96(t,J=7.2Hz,3H).13C NMR(75MHz,CDCl3)δ171.1,168.9,160.4,158.1,139.0,128.6,125.3,124.8,123.5,123.3,122.8,121.1,119.3,111.9,69.6,62.0,61.6,44.1,33.8,14.0,13.6.HRMS(ESI)m/z:[M+Na]+Calcd for407.0924C21H20O5SNa,found 407.0925.
实施例十三1-(叔丁基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的合成
向配备有搅拌棒的10mL Schlenk管中加入(0.2mmol)、溴丙二酸二乙酯(0.3mmol)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物1-(叔丁基)-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯,产率为80%。
产物的核磁数据和高分辨质谱:1H NMR(300MHz,CDCl3)δ7.50–7.35(m,2H),7.23–7.11(m,2H),4.40–4.29(m,1H),4.22–3.99(m,4H),3.99–3.85(m,1H),3.51–3.28(m,1H),1.29(t,J=7.2Hz,3H),1.20(t,J=7.1Hz,3H),1.03(s,9H).13C NMR(75MHz,CDCl3)δ171.6,169.6,159.4,159.2,127.2,122.8,122.7,122.0,120.7,111.7,68.5,61.9,61.5,55.4,36.1,34.0,28.5,13.8,13.7.HRMS(ESI)m/z:[M+Na]+Calcd for 381.1672C21H26O5Na,found381.1680.
实施例十四7-甲基-1-苯基-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的合成
向配备有搅拌棒的10mL Schlenk管中加入-甲基-2-(苯乙炔基)-1-(乙烯基氧基)苯(0.2mmol)、溴丙二酸二酯(0.3mmol)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物7-甲基-1-苯基-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯,产率为58%。
产物的核磁数据和高分辨质谱:1H NMR(300MHz,CDCl3)δ7.38(d,J=8.4Hz,1H),7.30–7.17(m,5H),7.04(d,J=7.3Hz,1H),6.90(s,1H),5.40(d,J=1.3Hz,1H),4.47–4.18(m,2H),4.14–3.95(m,1H),3.85–3.65(m,1H),3.50–3.30(m,2H),2.35(s,3H),1.33(t,J=7.1Hz,3H),0.89(t,J=7.2Hz,3H).13C NMR(75MHz,CDCl3)δ171.2,168.8,158.9,158.4,138.2,132.3,129.2,127.9,127.4,125.3,124.3,120.8,119.2,111.3,48.9,33.9,21.2,14.0,13.4.HRMS(ESI)m/z:[M+Na]+Calcd for 415.1516C24H24O5Na,found 415.1516.
实施例十五7-甲氧基-1-苯基-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的合成
向配备有搅拌棒的10mL Schlenk管中加入4-甲氧基-2-(苯乙炔基)-1-(乙烯基氧基)苯(0.2mmol)、溴丙二酸二乙酯(0.3mmol)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物7-甲氧基-1-苯基-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯,产率为52%。
产物的核磁数据和高分辨质谱:1H NMR(300MHz,CDCl3)δ7.34(d,J=9.0Hz,1H),7.25–7.14(m,5H),6.78(dd,J=9.0,2.6Hz,1H),6.51(d,J=2.6Hz,1H),5.37(s,1H),4.41–4.16(m,2H),4.04–3.90(m,1H),3.79–3.59(m,4H),3.44–3.24(m,2H),1.29(t,J=7.1Hz,3H),0.85(t,J=7.2Hz,3H).13C NMR(75MHz,CDCl3)δ171.2,168.7,159.2,155.8,155.3,138.0,129.2,128.0,127.5,125.9,121.0,112.1,111.2,102.5,69.9,62.0,61.5,55.8,48.8,33.9,14.0,13.4.HRMS(ESI)m/z:[M+Na]+Calcd for 431.1465C24H24O6Na,found431.1465.实施例十六7-氟-1-苯基-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的合成
向配备有搅拌棒的10mL Schlenk管中加入4-氟-2-(苯乙炔基)-1-(乙烯基氧基)苯(0.2mmol)、溴丙二酸二乙酯(0.3mmol)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物7-氟-1-苯基-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯,产率为34%。
产物的核磁数据和高分辨质谱:1H NMR(300MHz,CDCl3)δ7.37(dd,J=9.0,4.1Hz,1H),7.25–7.15(m,5H),6.93–6.87(m,1H),6.72(dd,J=8.5,2.6Hz,1H),5.36(s,1H),4.42–4.17(m,2H),4.08–3.92(m,1H),3.86–3.58(m,1H),3.44–3.24(m,2H),1.29(t,J=7.1Hz,3H),0.83(t,J=7.2Hz,3H).13C NMR(75MHz,CDCl3)δ171.0,168.6,159.1(d,1JC-F=238.6Hz),160.3,156.6,137.7,129.1,128.1,127.6,126.0(d,3JC-F=10.8Hz),121.3(d,4JC-F=3.8Hz),112.3(d,3JC-F=9.7Hz),110.6(d,2JC-F=26.3Hz),105.2(d,2JC-F=25.4Hz),69.8,62.1,61.6,48.7,34.0,14.0,13.4.HRMS(ESI)m/z:[M+Na]+Calcd for419.1265C23H21O5FNa,found 419.1267.
实施例十七7-氯-1-苯基-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的合成
向配备有搅拌棒的10mL Schlenk管中加入4-氯-2-(苯乙炔基)-1-(乙烯基氧基)苯(0.2mmol)、溴丙二酸二乙酯(0.3mmol)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物7-氯-1-苯基-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯,产率为36%。
产物的核磁数据和高分辨质谱:1H NMR(300MHz,CDCl3)δ7.41(d,J=8.8Hz,1H),7.30–7.16(m,6H),7.07(d,J=2.1Hz,1H),5.40(s,1H),4.46–4.21(m,2H),4.11–3.98(m,1H),3.82–3.66(m,1H),3.49–3.30(m,2H),1.34(t,J=7.1Hz,3H),0.88(t,J=7.2Hz,3H).13C NMR(75MHz,CDCl3)δ171.0,168.6,160.0,158.8,137.7,129.1,128.5,128.1,127.6,126.5,123.4,120.8,119.0,112.8,62.1,61.6,48.7,33.9,14.0,13.4.HRMS(ESI)m/z:[M+Na]+Calcd for 435.0970C23H21O5ClNa,found 435.0970.
实施例十八6-氟-1-苯基-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯的合成
向配备有搅拌棒的10mL Schlenk管中加入4-氟-1-(苯乙炔基)-2-(乙烯基氧基)苯(0.2mmol)、溴丙二酸二乙酯(0.3mmol)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物6-氟-1-苯基-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二乙酯,产率为36%。
产物的核磁数据和高分辨质谱:1H NMR(500MHz,CDCl3)δ7.28–7.19(m,6H),6.99(dd,J=8.5,5.5Hz,1H),6.90–6.86(m,1H),5.39(d,J=1.3Hz,1H),4.43–4.21(m,2H),4.09–3.93(m,1H),3.77–3.65(m,1H),3.44–3.29(m,2H),1.32(t,J=7.1Hz,3H),0.86(t,J=7.2Hz,3H).13C NMR(125MHz,CDCl3)δ171.1,168.7,160.3(d,3JC-F=13.3Hz),160.1(d,1JC-F=241.5Hz),158.8(d,4JC-F=3.7Hz),137.9,129.2,128.0,127.6,121.7(d,5JC-F=1.5Hz),120.9,119.3(d,3JC-F=9.6Hz),110.8(d,2JC-F=23.6Hz),100.0(d,2JC-F=26.8Hz),70.0,62.1,61.5,48.9,34.0,14.0,13.4.HRMS(ESI)m/z:[M+Na]+Calcd for419.1265C23H21O5FNa,found 419.1265.
实施例十九10-苯基-8,10-二氢-9H-环戊[b]萘并[1,2-d]呋喃-9,9-二羧酸二乙酯的合成
向配备有搅拌棒的10mL Schlenk管中加入1-(苯乙炔基)-2-(乙烯基氧基)萘(0.2mmol)、溴丙二酸二乙酯(0.3mmol)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物10-苯基-8,10-二氢-9H-环戊[b]萘并[1,2-d]呋喃-9,9-二羧酸二乙酯,产率为55%。
产物的核磁数据和高分辨质谱:1H NMR(300MHz,CDCl3)δ7.88(d,J=8.1Hz,1H),7.69(s,2H),7.49–7.23(m,8H),5.70(d,J=1.8Hz,1H),4.50–4.11(m,3H),3.88–3.71(m,1H),3.58–3.38(m,2H),1.35(t,J=7.1Hz,3H),0.95(t,J=7.2Hz,3H).13C NMR(75MHz,CDCl3)δ171.2,168.7,157.7,157.4,138.5,130.4,129.4,128.23,128.19,127.7,127.0,125.8,124.7,124.3,122.6,120.7,112.8,62.1,61.6,49.8,33.7,14.0,13.5.HRMS(ESI)m/z:[M+Na]+Calcd for 451.1516C27H24O5Na,found 451.1522.
实施例二十1-苯基-1,3-二氢-2H-苯并[b]环戊[d]噻吩-2,2-二羧酸二乙酯的合成
向配备有搅拌棒的10mL Schlenk管中加入(2-(苯基乙炔基)苯基)(乙烯基)硫烷(0.2mmol)、溴丙二酸二乙酯(0.3mmol)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物10-苯基-8,10-二氢-9H-环戊[b]萘并[1,2-d]呋喃-9,9-二羧酸二乙酯,产率为78%。
产物的核磁数据和高分辨质谱:1H NMR(300MHz,CDCl3)δ7.76(d,J=7.8Hz,1H),7.25–7.06(m,8H),5.47(d,J=1.3Hz,1H),4.41–4.12(m,3H),3.83–3.67(m,1H),3.57–3.37(m,2H),1.28(t,J=7.1Hz,3H),0.87(t,J=7.1Hz,3H).13C NMR(75MHz,CDCl3)δ171.3,168.8,145.0,139.8,139.7,138.1,134.2,129.2,128.0,127.4,124.2,123.6,123.2,121.8,70.8,62.0,61.4,52.8,37.4,14.0,13.5.HRMS(ESI)m/z:[M+Na]+Calcd for417.1131C23H22O4SNa,found 417.1139.
实施例二十一1-苯基-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二异丙酯的合成
向配备有搅拌棒的10mL Schlenk管中加入1-(苯乙炔基)-2-(乙烯基氧基)苯(0.2mmol)、2-溴丙二酸二异丙酯(0.3mmol)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物1-苯基-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二异丙酯,产率为70%。
产物的核磁数据和高分辨质谱:1H NMR(300MHz,CDCl3)δ7.49(d,J=8.2Hz,1H),7.30–7.18(m,6H),7.17–7.03(m,2H),5.40(d,J=1.4Hz,1H),5.27–5.09(m,1H),4.65–4.36(m,1H),4.20–4.00(m,1H),3.48–3.26(m,1H),1.33(t,J=6.0Hz,6H),1.06(d,J=6.2Hz,3H),0.64(d,J=6.3Hz,3H).13C NMR(75MHz,CDCl3)δ170.7,168.3,160.4,158.2,138.3,129.3,128.0,127.4,125.3,123.2,122.7,121.6,119.2,111.8,69.8,69.52,69.46,48.8,34.3,21.6,21.5,21.3,20.7.HRMS(ESI)m/z:[M+Na]+Calcd for 429.1672C25H26O5Na,found429.1680.
实施例二十二1-苯基-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二甲酯的合成
向配备有搅拌棒的10mL Schlenk管中加入1-(苯乙炔基)-2-(乙烯基氧基)苯(0.2mmol)、溴丙二酸二甲酯(0.3mmol)、fac-Ir(ppy)3(1mol%)和DMF(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物1-苯基-1,3-二氢-2H-环戊[b]苯并呋喃-2,2-二羧酸二甲酯,产率为40%。
产物的核磁数据和高分辨质谱:1H NMR(400MHz,CDCl3)δ7.49(d,J=8.3Hz,1H),7.28–7.20(m,6H),7.15–7.06(m,2H),5.43(d,J=1.1Hz,1H),4.09–3.94(m,1H),3.85(s,3H),3.45–3.34(m,1H),3.12(s,3H).13C NMR(75MHz,CDCl3)δ171.6,169.1,160.5,158.3,137.9,129.1,128.0,127.5,125.3,123.3,122.9,120.8,119.3,111.9,70.1,53.2,52.1,49.1,33.9.
实施例二十三溶剂的筛选
向配备有搅拌棒的10mLSchlenk管中加入1-(苯乙炔基)-2-(乙烯基氧基)苯(0.2mmol)、溴丙二酸二乙酯(0.3mmol)和溶剂(2mL),将Schlenk管抽真空并用氩气置换3次,然后将其拧紧。将反应混合物在室温下在可见光(λmax=405nm)的照射下搅拌36小时。真空蒸发溶剂,残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(5:1)洗脱,得到产物1-苯基-1,3-二氢-2H-环戊二烯[b]苯并呋喃-2,2-二羧酸二乙酯。
表1不同溶剂下产物的产率
序号 | 溶剂 | 产率(%) |
1 | DMF | 74 |
2 | DCM | trace |
3 | MeCN | trace |
4 | CHCl3 | trace |
5 | 1,4-dioxane | trace |
6 | DCE | trace |
7 | DMSO | trace |
8 | MeOH | trace |
9 | toluene | trace |
10 | THF | trace |
实施例二十四1,6-烯炔的制备
将式A所示的苯酚和1,2-二溴乙烷(3equiv)加入乙腈(50mL)中,然后加入K2CO3(3equiv),将所得混合物搅拌并在室温下过夜,用水(10mL)淬灭反应,通过旋转蒸发仪减压浓缩。用CH2Cl2(20mL×3)萃取,有机层用盐水(10mL)洗涤,经Mg2SO4干燥并通过旋转蒸发仪减压浓缩。残余物通过快速柱色谱纯化,用石油醚和乙酸乙酯(20:1)洗脱,得到白色固体化合物B。
将化合物B在DMSO(10mL)中于在0℃下搅拌。向该搅拌溶液中分批加入tBuOK(2equiv)。将所得混合物在室温搅拌2小时。反应被淬灭用水(100mL)淬灭,用CH2Cl2(50mL×4)萃取。合并的有机层用盐水(100mL)洗涤,经Mg2SO4干燥并通过旋转蒸发器浓缩减压。粗产物通过硅胶柱色谱使用石油醚为展开剂纯化,得到1-碘-2-(乙烯基氧基)苯,为黄色油状物C,收率为68%。
将化合物C和取代的乙炔(1.2equiv)置于Et3N(8mL)中,在氩气保护下加入PdCl2(PPh3)2(0.02equiv)和CuI(0.04equiv)。将所得混合物在室温下搅拌6小时。过滤反应混合物并用CH2Cl2洗涤。将合并的滤液减压浓缩,残余物通过硅胶柱色谱纯化,使用石油醚洗脱。得到化合物D1,6-烯炔。
表2不同取代基下制备的1,6-烯炔
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实施例二十五溴丙二酸二异丙酯的制备
在超干的50mL圆底烧瓶中放入磁子,将丙二酸二异丙酯(1mmol)溶于10mL的DCM中,反应溶液加入NBS(1.2equiv),在30分钟逐滴滴加DBU(1.5equiv)。采用薄层色谱(TLC)监测反应。反应混合物用饱和氯化铵淬灭,用二氯甲烷萃取。有机层用硫酸镁干燥后过滤。溶剂真空蒸发,用柱层析法(PE/EA=10/1)纯化,得到相应溴丙二酸二异丙酯。
以上所述之实施例,只是本发明的较佳实施例而已,并非限制本发明的实施范围,故凡依本发明专利范围所述的构造、特征及原理所做的等效变化或修饰,均应包括于本发明申请专利范围内。
Claims (8)
1.可见光介导的环戊[b]苯并呋喃衍生物的合成方法,其特征在于,包括以下内容:
将式1所示的1,6-烯炔和式2所示的溴丙二酸二酯加入溶剂中,在室温和惰性气氛下,于可见光条件下反应,合成式3所示的环戊[b]苯并呋喃衍生物;
合成路线如下:
其中:X为O,S;R1选自氢、甲基、甲氧基、卤素或稠环;R2选自烷基、杂芳基或取代芳基,所述取代芳基为氢、氰基、卤素、苯基、甲氧基、直链烷基取代芳基;R3选自直链烷基;
所述溶剂为DMF;
所述可见光的波长为405nm。
2.根据权利要求1所述的可见光介导的环戊[b]苯并呋喃衍生物的合成方法,其特征在于,所述惰性气氛为氩气。
3.根据权利要求1所述的可见光介导的环戊[b]苯并呋喃衍生物的合成方法,其特征在于,所述光照条件为紫光、白炽灯光或氙灯光。
4.根据权利要求1所述的可见光介导的环戊[b]苯并呋喃衍生物的合成方法,其特征在于,式1所示的1,6-烯炔和式2所示的溴丙二酸二酯的摩尔比为1:1.5。
5.根据权利要求1所述的可见光介导的环戊[b]苯并呋喃衍生物的合成方法,其特征在于,所述溶剂的加入量均为式1所示的1,6-烯炔的1000mol%。
6.根据权利要求1所述的可见光介导的环戊[b]苯并呋喃衍生物的合成方法,其特征在于,反应中还加入光敏剂。
7.根据权利要求6所述的可见光介导的环戊[b]苯并呋喃衍生物的合成方法,其特征在于,所述光敏剂为fac-Ir(ppy)3。
8.根据权利要求6所述的可见光介导的环戊[b]苯并呋喃衍生物的合成方法,其特征在于,所述光敏剂的加入量为式1所示的1,6-烯炔的1mol%。
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