CN106316811B - 二环[3.n.1]化合物及其制备方法 - Google Patents

二环[3.n.1]化合物及其制备方法 Download PDF

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CN106316811B
CN106316811B CN201510320079.0A CN201510320079A CN106316811B CN 106316811 B CN106316811 B CN 106316811B CN 201510320079 A CN201510320079 A CN 201510320079A CN 106316811 B CN106316811 B CN 106316811B
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祝诗发
张巧慧
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Abstract

本发明公开一种二环[3.n.1]化合物及其制备方法，属于有机化学合成领域。本发明将炔酮化合物溶解于溶剂中，加入催化剂，0～120℃反应0.5h～40h后分离纯化，得到二环[3.n.1]化合物。其中，催化剂与炔酮化合物的摩尔比为0.01～1:1；溶剂与炔酮化合物的体积摩尔比为1～15mL:1mmol。本发明的制备方法具有操作简单快捷、反应过程对空气和水不敏感、所用催化剂用量少且廉价易得、纯化简单等优点。

Description

二环[3.n.1]化合物及其制备方法
技术领域
本发明属于有机化学合成领域，特别涉及一种二环[3.n.1]化合物及其制备方法。
背景技术
二环[3.n.1]化合物的制备方法：
方法一(Chem.Lett.1979,7,837-840)：
Figure BDA0000735928320000011
方法二(J.Am.Chem.Soc.1982,104,5808-5810)：
Figure BDA0000735928320000012
方法三(J.Am.Chem.Soc.1989,111,3701-3712)：
Figure BDA0000735928320000013
方法四(Org.Lett.2011,13,664-667)：
上述制备二环[3.n.1]化合物的方法中，方法一对底物的适用性不广泛；方法二所用催化剂不经济实用；方法三中生成的产物存在异构体，选择性差，产率较低；方法四中的原料合成复杂会给实际应用带来很大不便。
发明内容
为了克服现有技术的缺点与不足，本发明的首要目的在于提供一种二环[3.n.1]化合物。
本发明的另一目的在于提供上述二环[3.n.1]化合物的制备方法。该制备方法简单有效。
本发明的目的通过下述技术方案实现：
二环[3.n.1]化合物，结构式如下：
Figure BDA0000735928320000021
式中：R1为氢、烷基、酯基、酰基、苄基或取代的苄基等；其中，所述的取代的苄基的苯环上的取代基优选为苯基、卤素、烷基、烷氧基、羟基、酰基和胺基等中的至少一种常见取代基。
R2为苯基乙烯基类、苯基乙炔基类或芳基等；其中，R2上的苯环上的取代基优选为苯基、卤素、烷基、烷氧基、羟基、酰基和胺基等中的至少一种常见取代基；
R3为氢或烷基；优选为氢或C1～C200的烷基；更优选为C1～C50的烷基；更优选为氢或戊基；
C1-C2…Cn为链长为n个碳的取代或非取代碳链，其中n＝2～9的自然数，所述的取代的取代基可以为氢、烷基、环烷基和氧原子等中的至少一种常见取代基。
所述的二环[3.n.1]化合物的制备方法，包括如下步骤：
将炔酮化合物溶解于溶剂中，加入催化剂，反应后分离纯化，得到二环[3.n.1]化合物。
所述的二环[3.n.1]化合物的制备反应过程如下：
Figure BDA0000735928320000022
所述的炔酮化合物，其结构式如下：
Figure BDA0000735928320000031
式中：R1为氢、烷基、酯基、酰基、苄基或取代的苄基等；其中，所述的取代的苄基的苯环上的取代基优选为苯基、卤素、烷基、烷氧基、羟基、酰基和胺基等中的至少一种常见取代基。
R2为苯基乙烯基类、苯基乙炔基类或芳基等；其中，R2上的苯环上的取代基优选为苯基、卤素、烷基、烷氧基、羟基、酰基和胺基等中的至少一种常见取代基；
R3为氢或烷基；优选为氢或C1～C200的烷基；更优选为C1～C50的烷基；更优选为氢或戊基；
C1-C2…Cn为链长为n个碳的取代或非取代碳链，其中n＝2～9的自然数，所述的取代的取代基可以为氢、烷基、环烷基和氧原子等中的至少一种常见取代基。
所述的催化剂优选为Cu(OTf)2(II)、Fe(OTf)3(III)、Fe(OTf)2(II)、Bi(OTf)3、Sn(OTf)2、In(OTf)3、AgOTf、Zn(OTf)2、Yb(OTf)3(III)、FeCl3、InCl3、AgNTf2、AgSbF6、Fe(acac)3、氮杂卡宾金络合物(NHC-Au)、膦金络合物、HOTf、MsOH和TsOH中的至少一种；
所述的氮杂卡宾金络合物优选为IMesAuCl、IMesAuCl3、SIMesAuCl、IPrAuCl和SIPrAuCl等中的至少一种；
所述的膦金络合物优选为Ph3PAuCl和[JohnPhosAuSbF6]MeCN中至少一种；
所述的催化剂与炔酮化合物的摩尔比优选为0.01～1:1；
所述的溶剂优选为1,2-二氯乙烷(1,2-dichloroethane，DCE)、二氯甲烷(DCM)、硝基甲烷和甲苯中的任意一种；
所述的溶剂与炔酮化合物的体积摩尔比为1～15mL:1mmol。
所述的反应的条件优选为0～120℃反应0.5h～40h。
二环[3.n.1]化合物是很多重要天然产物的核心骨架，如Enaimeone A，Garcinol，β-Caryolanol，Taxol等。该类天然产物大多具有一定的生物活性。本 发明提供一种方便简单高效的方法一步构建[3.n.1]骨架。
Figure BDA0000735928320000041
本发明相对于现有技术，具有如下的优点及效果：
(1)本发明制备过程简单快捷，只通过简单的一步就能够高效地合成二环[3.n.1]化合物。
(2)本发明操作简单，反应过程对空气和水不敏感，所采用的原料易制备，所采用的催化剂用量少且廉价易得。
(3)本发明制备的二环[3.n.1]化合物纯化简单。
具体实施方式
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。
实施例1
Figure BDA0000735928320000042
在烧瓶中加入磁子，加入A1(56.5mg，0.25mmol)，1,2-二氯乙烷1.5mL，HOTf(37.5mg，0.25mmol)在室温(room temperature，rt)下搅拌1小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比10:1)纯化，即可得到产物B1(53.7mg，97％)：淡黄色固体，熔点125～127℃。1H NMR(400MHz,CDCl3)δ7.34(s,5H),5.88(s,1H),3.63(d,J＝6.7Hz,1H),3.09(d,J＝18.3Hz,1H),2.96–2.80(m,2H),2.73(d,J＝17.8Hz,1H),1.21(s,3H).13C NMR(101MHz,CDCl3)δ213.3,211.2,144.9,138.0,128.8,128.2,125.5,121.1,57.2,50.2,48.4,45.9,12.4.IR(KBr)νmax 3028,2977,2932,2833,1774,1730,1681,1494,1447,1403,1347,1278,1086,1051,759,697cm-1.HRMS(EI)calcd forC15H14O2[M]+:226.0988,found:m/z 226.0988.
实施例2
Figure BDA0000735928320000051
在烧瓶中加入磁子，加入A2(60mg，0.25mmol)，二氯甲烷0.25mL，HOTf(37.5mg，0.25mmol)在室温下搅拌2小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比20:1)纯化，即可得到产物B2(50.0mg，83％)：白色固体，熔点128～130℃，1HNMR(400MHz,CDCl3)δ7.41–7.25(m,5H),5.87(s,1H),3.61(d,J＝6.8Hz,1H),3.10(d,J＝18.1Hz,1H),2.89–2.70(m,3H),1.78(dt,J＝25.8,7.1Hz,2H),0.88(t,J＝7.4Hz,3H).13CNMR(101MHz,CDCl3)δ213.5,211.6,145.0,138.0,128.8,128.2,125.4,121.1,61.7,50.8,48.7,44.9,21.4,9.1.IR(KBr)νmax 2922,1771,1730,1493,1441,1349,1278,1066,763,740,695cm-1.HRMS(EI)calcd for C16H16O2[M]+:240.1145,found:m/z 240.1145.
实施例3
Figure BDA0000735928320000052
在烧瓶中加入磁子，加入A3(67.0mg，0.25mmol)，1,2-二氯乙烷1.5mL，HOTf(37.5mg，0.25mmol)在室温下搅拌1小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比5:1)纯化，即可得到产物B3(62.3mg，93％)：淡黄色固体，熔点90～92℃，1H NMR(400MHz,CDCl3)δ7.43–7.24(m,5H),5.86(s,1H),3.60(d,J＝6.8Hz,1H),3.08(d,J＝18.0Hz,1H),2.79(ddd,J＝30.4,22.5,12.2Hz,3H),1.71(dt,J＝13.1,11.6Hz,2H),1.39–1.20(m,3H),1.14(t,J＝8.5Hz,1H),0.89(t,J＝6.8Hz,3H).13C NMR(101MHz,CDCl3)δ213.6,211.7,145.0,138.0,128.7,128.2,125.4,121.1,61.2,50.7,48.7,45.3,28.3,26.8,23.3,13.8.IR(KBr)νmax 2961,2929,2865,1775,1731,1496,1440,1401,1345,1105,1070,1034,762,695cm-1.HRMS(ESI)calcd for C18H21O2[M+H]+:269.1536,found:m/z269.1535.
实施例4
在烧瓶中加入磁子，加入A4(77.5mg，0.25mmol)，1,2-二氯乙烷0.5mL，HOTf(37.5mg，0.25mmol)在室温下搅拌1小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比5:1)纯化，即可得到产物B4(76.0mg，98％)：淡黄色固体，熔点98～100℃，1H NMR(400MHz,CDCl3)δ7.43–7.30(m,5H),5.88(s,1H),3.63(d,J＝6.8Hz,1H),3.11(d,J＝18.0Hz,1H),2.86(dd,J＝18.1,6.7Hz,1H),2.82–2.72(m,2H),1.83–1.67(m,2H),1.23(dd,J＝49.7,4.9Hz,12H),0.90(t,J＝6.5Hz,3H).13C NMR(101MHz,CDCl3)δ213.7,211.7,145.0,138.0,128.7,128.2,125.4,121.1,61.2,50.7,48.7,45.3,31.7,30.2,29.0,28.7,24.7,22.6,14.1.IR(KBr)νmax 2959,2927,2854,1775,1731,1495,1464,1440,1403,1073,1031,975,762,695cm-1.HRMS(ESI)calcd for C21H27O2[M+H]+:311.2006,found:m/z311.2003.
实施例5
在烧瓶中加入磁子，加入A5(75.5mg，0.25mmol)，1,2-二氯乙烷1.5mL，HOTf(37.5mg，0.25mmol)在室温下搅拌2小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比5:1)纯化，即可得到产物B5(65.7mg，87％)：淡黄色固体，熔点113～115℃。1H NMR(400MHz,CDCl3)δ7.31(dd,J＝11.6,6.7Hz,7H),7.27–7.20(m,2H),7.18(d,J＝7.2Hz,1H),5.86(s,1H),3.55(d,J＝6.8Hz,1H),3.16(d,J＝14.0Hz,1H),3.07–2.96(m,2H),2.82(d,J＝3.9Hz,2H),2.61(dd,J＝17.9,6.8Hz,1H).13C NMR(101MHz,CDCl3)δ212.9,210.8,145.1,137.9,136.6,130.7,128.8,128.3,128.2,126.6,125.4,121.0,62.4,50.6,48.6,45.3,33.8.IR(KBr)νmax 3029,2917,2831,1775,1731,1599,1494,1442,1400,1351,1273,1074,1032,759,700,650cm-1.HRMS(ESI)calcd for C21H19O2[M+H]+:303.1380,found:m/z 303.1377.
实施例6
Figure BDA0000735928320000071
在烧瓶中加入磁子，加入A6(60.0mg，0.25mmol)，1,2-二氯乙烷1.5mL，HOTf(1.9mg，0.0125mmol)在80℃下搅拌6小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比15:1)纯化。即可得到产物B6(48.0mg，80％)：橘黄色固体，熔点113～115℃，1H NMR(400MHz,CDCl3)δ7.23(d,J＝7.6Hz,2H),7.15(d,J＝7.8Hz,2H),5.84(s,1H),3.61(d,J＝6.8Hz,1H),3.07(d,J＝18.3Hz,1H),2.95–2.78(m,2H),2.72(d,J＝17.7Hz,1H),2.35(s,3H),1.20(s,3H).13C NMR(101MHz,CDCl3)δ213.5,211.4,144.8,138.2,135.1,129.4,125.3,120.1,57.2,50.2,48.4,45.9,21.1,12.4.IR(KBr)νmax 3029,2977,2928,1772,1728,1511,1451,1402,1382,1346,1275,1120,1048,981,844,811,775,738cm-1.HRMS(ESI)calcd for C16H17O2[M+H]+:241.1223,found:m/z 241.1222.
实施例7
在烧瓶中加入磁子，加入A7(64.0mg，0.25mmol)，硝基甲烷1.5mL，HOTf(37.5mg，0.25mmol)在室温下搅拌1小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比10:1)纯化，即可得到产物B7(57.0mg，89％)：白色固体，熔点129～130℃，1HNMR(400MHz,CDCl3)δ7.27(d,J＝7.4Hz,2H),6.88(d,J＝7.7Hz,2H),5.78(s,1H),3.81(s,3H),3.60(d,J＝6.7Hz,1H),3.07(d,J＝18.2Hz,1H),2.95–2.78(m,2H),2.72(d,J＝17.6Hz,1H),1.20(s,3H).13C NMR(101MHz,CDCl3)δ213.6,211.4,159.7,144.4,130.5,126.7,119.2,114.1,57.2,55.4,50.1,48.4,45.9,12.4.IR(KBr)νmax 2970,2931,2836,1773,1730,1605,1511,1454,1405,1347,1250,1182,1117,1031,823,779,616cm-1.HRMS(ESI)calcd for C16H17O3[M+H]+:257.1172,found:m/z 257.1170.
实施例8
在烧瓶中加入磁子，加入A8(61.0mg，0.25mmol)，1,2-二氯乙烷3.75mL，HOTf(37.5mg，0.25mmol)在室温下搅拌1小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比15:1)纯化，即可得到产物B8(53.0mg，87％)：橘黄色固体，熔点148～150℃，1H NMR(400MHz,CDCl3)δ7.31(dd,J＝7.4,5.5Hz,2H),7.04(t,J＝8.2Hz,2H),5.83(s,1H),3.58(d,J＝6.8Hz,1H),3.08(d,J＝18.2Hz,1H),2.96–2.79(m,2H),2.73(d,J＝17.7Hz,1H),1.21(s,3H).13C NMR(101MHz,CDCl3)δ213.1,211.0,162.6(d,JC-F＝251.3Hz),143.96,134.2(d,JC-F＝3.5Hz),127.2(d,JC-F＝8.1Hz),121.0,115.7(d,JC-F＝21.7Hz),57.1,50.1,48.5,45.7,12.4.19F NMR(376MHz,CDCl3)δ-113.43.IR(KBr)νmax3113,2920,2847,1773,1730,1598,1507,1390,1271,1226,1159,1093,1047,817,776,735,614cm- 1.HRMS(ESI)calcd for C15H14FO2[M+H]+:245.0972,found:m/z245.0971.
实施例9
Figure BDA0000735928320000082
在烧瓶中加入磁子，加入A9(65.0mg，0.25mmol)，1,2-二氯乙烷1.5mL，HOTf(37.5mg，0.25mmol)在0℃下搅拌12小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比5:1)纯化，即可得到产物B9(64.4mg，99％)：淡黄色固体，熔点135～137℃，1H NMR(400MHz,CDCl3)δ7.32(d,J＝8.0Hz,2H),7.26(d,J＝7.8Hz,2H),5.88(s,1H),3.57(d,J＝6.8Hz,1H),3.07(d,J＝18.2Hz,1H),2.98–2.79(m,2H),2.73(d,J＝17.9Hz,1H),1.21(s,3H).13C NMR(101MHz,CDCl3)δ212.9,210.9,143.9,136.4,134.2,128.9,126.7,121.7,57.1,50.1,48.3,45.7,12.4.IR(KBr)νmax 2932,1775,1732,1492,1450,1401, 1348,1280,1092,1049,1012,817,778,727cm-1.HRMS(ESI)calcd forC15H14ClO2[M+H]+:261.0677,found:m/z 261.0674.
实施例10
Figure BDA0000735928320000091
在烧瓶中加入磁子，加入A10(63.0mg，0.25mmol)，1,2-二氯乙烷1.5mL，HOTf(37.5mg，0.25mmol)在室温下搅拌0.5小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比1:1)纯化，即可得到产物B10(43.5mg，69％)：淡黄色固体，熔点150～152℃，1H NMR(400MHz,CDCl3)δ7.18(d,J＝7.8Hz,2H),6.80(d,J＝8.0Hz,2H),5.88(s,1H),5.76(s,1H),3.58(d,J＝6.5Hz,1H),3.07(d,J＝18.2Hz,1H),2.98–2.80(m,2H),2.72(d,J＝17.6Hz,1H),1.20(s,3H).13C NMR(101MHz,CDCl3)δ214.2,211.8,156.0,144.3,130.4,126.9,119.1,115.6,57.4,50.1,48.4,46.0,12.4.IR(KBr)νmax 3395,2975,2928,1769,1725,1674,1608,1514,1441,1350,1270,1215,1176,1111,1051,825,780cm-1.HRMS(ESI)calcd for C15H15O3[M+H]+:243.1016,found:m/z 243.1014.
实施例11
在烧瓶中加入磁子，加入A11(70.7mg，0.25mmol)，1,2-二氯乙烷1.5mL，AgNTf2(4.8mg，0.0125mmol)和HOTf(1.9mg，0.0125mmol)在室温下搅拌12小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比1:1)纯化，即可得到产物B11(42.5mg，60％)：无色油状液体，1H NMR(400MHz,CDCl3)δ7.69(s,1H),7.50(d,J＝8.0Hz,2H),7.26(d,J＝8.9Hz,2H),5.84(s,1H),3.59(d,J＝6.6Hz,1H),3.06(d,J＝18.2Hz,1H),2.96–2.79(m, 2H),2.77–2.65(m,1H),2.18(s,3H),1.20(s,3H).13C NMR(101MHz,CDCl3)δ213.5,211.3,168.6,144.2,138.0,133.7,126.0,120.4,120.0,57.2,50.1,48.2,45.9,24.5,12.4.IR(KBr)νmax 3106,2927,1772,1728,1669,1595,1528,1405,1379,1318,1255,1118,1093,821cm-1.HRMS(ESI)calcd for C17H18NO3[M+H]+:284.1281,found:m/z284.1279.
实施例12
Figure BDA0000735928320000101
在烧瓶中加入磁子，加入A12(69.0mg，0.25mmol)，1,2-二氯乙烷1.5mL，加入AgNTf2(4.8mg，0.0125mmol)和HOTf(1.9mg，0.0125mmol)在室温下搅拌12小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比7:1)纯化，即可得到产物B12(55.2mg，80％)：无色油状液体， 1H NMR(400MHz,CDCl3)δ7.87–7.72(m,3H),7.47(dt,J＝14.6,7.0Hz,2H),7.36(t,J＝7.6Hz,1H),7.25(d,J＝6.8Hz,1H),5.64(s,1H),3.42(d,J＝6.8Hz,1H),3.06(d,J＝18.4Hz,1H),2.79(s,2H),2.70(dd,J＝18.4,6.9Hz,1H),1.20(s,3H).13C NMR(101MHz,CDCl3)δ213.5,211.7,146.4,137.4,133.8,130.6,128.7,128.6,126.8,126.2,125.8,125.3,125.3,124.4,57.1,50.8,49.8,46.1,12.5.IR(KBr)νmax 2929,1773,1730,1506,1451,1397,1345,1106,1050,980,776,736cm-1.HRMS(ESI)calcd forC19H17O2[M+H]+:277.1223,found:m/z 277.1221.
实施例13
Figure BDA0000735928320000102
在烧瓶中加入磁子，加入A13(62.5mg，0.25mmol)，1,2-二氯乙烷3.75mL，加入AgNTf2(4.8mg，0.0125mmol)和HOTf(1.9mg，0.0125mmol)在120℃条件下搅拌40小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚： 乙酸乙酯体积比6:1)纯化，即可得到产物B13(25.0mg，40％)：白色固体，熔点153～155℃，1H NMR(400MHz,CDCl3)δ7.43(d,J＝4.0Hz,2H),7.34(s,3H),6.00(s,1H),3.34(d,J＝6.7Hz,1H),3.17(d,J＝18.4Hz,1H),2.89–2.72(m,2H),2.68(d,J＝18.4Hz,1H),1.18(s,3H).13C NMR(101MHz,CDCl3)δ211.5,210.6,131.6,130.6,128.8,128.4,127.8,122.3,90.1,86.6,56.7,49.9,49.9,45.6,12.5.IR(KBr)νmax 3113,2928,1770,1722,1489,1452,1389,1345,1106,1047,980,931,759,691cm-1.HRMS(ESI)calcd for C17H15O2[M+H]+:251.1067,found:m/z251.1065.
实施例14
Figure BDA0000735928320000111
在烧瓶中加入磁子，加入A14(63.0mg，0.25mmol)，1,2-二氯乙烷1.5mL，加入AgNTf2(4.8mg，0.0125mmol)和HOTf(1.9mg，0.0125mmol)在室温下搅拌12小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比6:1)纯化，即可得到产物B14(26.6mg，42％)：白色固体，熔点165～167℃，1H NMR(400MHz,CDCl3)δ7.41(d,J＝7.6Hz,2H),7.33(t,J＝7.4Hz,2H),7.30–7.22(m,1H),6.71(d,J＝16.2Hz,1H),6.56(d,J＝16.2Hz,1H),5.66(s,1H),3.65(d,J＝6.6Hz,1H),2.98(d,J＝18.3Hz,1H),2.93–2.79(m,2H),2.73(d,J＝17.8Hz,1H),1.19(s,3H).13C NMR(101MHz,CDCl3)δ213.8,211.2,143.8,136.4,128.8,128.1,128.1,126.9,126.6,124.5,57.1,49.7,45.9,45.1,12.5.IR(KBr)νmax1769,1726,1452,1390,1345,1051,969,692cm-1.HRMS(ESI)calcd for C17H17O2[M+H]+:253.1223,found:m/z 253.1221.
实施例15
Figure BDA0000735928320000112
在烧瓶中加入磁子，加入A15(70.5mg，0.25mmol)，1,2-二氯乙烷0.25mL， 加入AgNTf2(4.8mg，0.0125mmol)和HOTf(1.9mg，0.0125mmol)在室温下搅拌12小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比20:1)纯化，即可得到产物B15(63.5mg，90％)：无色液体，1H NMR(400MHz,CDCl3)δ7.37(m,4H),7.33–7.24(m,1H),6.35(s,1H),3.49(s,1H),3.36(d,J＝19.4Hz,1H),2.58(dd,J＝19.4,3.1Hz,1H),2.33(s,3H),2.25(t,J＝11.9Hz,1H),2.14–1.92(m,4H),1.75(d,J＝12.2Hz,1H).13C NMR(101MHz,CDCl3)δ212.4,207.7,138.6,136.7,128.6,127.7,125.6,124.4,61.5,50.4,38.7,37.1,32.7,27.9,17.6.IR(KBr)νmax 2938,2863,1712,1494,1447,1357,1273,1226,1043,886,757,698.HRMS(EI)calcd for C17H18O2[M]+:254.1301,found:m/z254.1297.
实施例16
Figure BDA0000735928320000121
在烧瓶中加入磁子，加入A16(63.5mg，0.25mmol)，1,2-二氯乙烷1.5mL，加入AgNTf2(4.8mg，0.0125mmol)和HOTf(1.9mg，0.0125mmol)在室温下搅拌12小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比30:1)纯化，即可得到产物B16(57.1mg，90％)：淡黄色固体，熔点73～75℃，1H NMR(400MHz,CDCl3)δ7.44–7.30(m,4H),7.30–7.22(m,1H),6.32(s,1H),3.50–3.30(m,2H),3.02(dt,J＝13.1,6.4Hz,1H),2.53(dd,J＝19.4,2.4Hz,1H),2.30(dd,J＝16.4,9.5Hz,1H),2.11–1.88(m,4H),1.81–1.59(m,1H),1.15(dd,J＝10.4,6.8Hz,6H).13C NMR(101MHz,CDCl3)δ214.9,212.9,138.6,136.6,128.6,127.7,125.6,124.6,62.5,50.6,38.4,37.9,36.9,32.5,20.1,20.0,17.5.IR(KBr)νmax3029,2937,2869,1711,1495,1448,1356,1219,1138,1019,980,889,758,696.HRMS(EI)calcd for C19H22O2[M]+:282.1614,found:m/z 282.1611.
实施例17
Figure BDA0000735928320000122
在烧瓶中加入磁子，加入A17(67.5mg，0.25mmol)，1,2-二氯乙烷1.5mL，加入AgNTf2(4.8mg，0.0125mmol)和HOTf(1.9mg，0.0125mmol)在室温下搅拌12小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比7:1)纯化，即可得到产物B17(56.7mg，84％)：无色液体，1H NMR(400MHz,CDCl3)δ7.41–7.22(m,5H),6.29(s,1H),3.80(s,3H),3.55(d,J＝19.0Hz,1H),3.49(s,1H),2.69(dd,J＝19.3,3.6Hz,1H),2.43(t,J＝13.5Hz,1H),2.14–1.87(m,4H),1.78–1.59(m,1H).13C NMR(101MHz,CDCl3)δ209.8,172.5,138.7,136.3,128.6,127.6,125.6,124.4,57.7,52.6,49.7,39.1,38.3,32.4,17.5.IR(KBr)νmax 2948,2862,1742,1714,1442,1394,1282,1233,1072,760,695cm-1.HRMS(ESI)calcd for C17H19O3[M+H]+:271.1329,found:m/z 271.1327.
实施例18
Figure BDA0000735928320000131
在烧瓶中加入磁子，加入A18(49.5mg，0.25mmol)，1,2-二氯乙烷1.5mL，加入AgNTf2(4.8mg，0.0125mmol)和HOTf(1.9mg，0.0125mmol)在室温下搅拌5小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比10:1)纯化，即可得到产物B18(27.5mg，55％)：淡黄色液体， 1H NMR(400MHz,CDCl3)δ7.34(m,5H),5.92(s,1H),3.02(d,J＝27.8Hz,2H),2.68(d,J＝17.2Hz,1H),2.41(s,1H),2.32(t,J＝9.7Hz,1H),2.25(d,J＝7.2Hz,2H),1.94(d,J＝10.6Hz,1H).13C NMR(101MHz,CDCl3)δ217.4,143.9,139.4,128.5,127.5,125.5,121.3,47.8,42.1,41.4,30.4,26.0.IR(KBr)νmax 2922,2852,2361,2336,1746,1649,1522,1272,750cm-1.HRMS(ESI)calcd for C14H15O[M+H]+:199.1117,found:m/z199.1116.
实施例19
Figure BDA0000735928320000132
在烧瓶中加入磁子，加入A19(53.0mg，0.25mmol)，1,2-二氯乙烷1.5mL， 加入AgNTf2(4.8mg，0.0125mmol)和HOTf(1.9mg，0.0125mmol)在室温下搅拌12小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比10:1)纯化，即可得到产物B19(38.7mg，73％)：无色液体，1H NMR(400MHz,CDCl3)δ7.46–7.18(m,5H),6.29(s,1H),3.40(s,1H),2.88(dd,J＝19.9,4.6Hz,1H),2.70–2.44(m,2H),1.94(d,J＝11.5Hz,4H),1.57(s,2H).13C NMR(101MHz,CDCl3)δ216.0,139.3,137.1,128.5,127.4,125.8,125.7,49.9,44.5,36.9,35.8,32.6,17.2.IR(KBr)νmax 2925,2852,2361,1715,1650,1540,1442,1262,751,693cm-1.HRMS(ESI)calcd for C15H17O[M+H]+:213.1274,found:m/z213.1272.
实施例20
Figure BDA0000735928320000141
在烧瓶中加入磁子，加入A20(56.5mg，0.25mmol)，1,2-二氯乙烷1.5mL，加入AgNTf2(4.8mg，0.0125mmol)和HOTf(1.9mg，0.0125mmol)在室温下搅拌12小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：二氯甲烷体积比1:1)纯化，即可得到产物B20(41.2mg，73％)：无色液体，1H NMR(400MHz,CDCl3)δ7.31(m,5H),6.01(s,1H),3.55(s,1H),2.82(s,1H),2.68(d,J＝17.8Hz,1H),2.42(dd,J＝18.4,4.7Hz,1H),2.20(dd,J＝20.4,11.8Hz,1H),1.78(t,J＝14.2Hz,2H),1.61(s,1H),1.46(t,J＝13.2Hz,1H),1.39–1.23(m,2H),1.10(dd,J＝25.9,13.2Hz,1H).13C NMR(101MHz,CDCl3)δ215.1,139.9,139.8,128.5,127.4,126.4,124.9,50.9,46.1,34.2,30.9,29.4,26.8,26.0.IR(KBr)νmax 2925,2851,2360,2336,1710,1646,1491,1265,746,697cm-1.HRMS(ESI)calcd for C16H19O[M+H]+:227.1430,found:m/z 227.1428.
实施例21
Figure BDA0000735928320000142
在烧瓶中加入磁子，加入A21(60mg，0.25mmol)，甲苯1.5mL，加入 AgNTf2(4.8mg，0.0125mmol)和HOTf(1.9mg，0.0125mmol)在室温下搅拌12小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：二氯甲烷体积比1:1)纯化，即可得到产物B21(45.0mg，75％)：无色液体，1H NMR(400MHz,CDCl3)δ7.32(m,5H),6.00(s,1H),3.47(s,1H),2.76(d,J＝18.5Hz,1H),2.65(d,J＝7.1Hz,1H),2.47(d,J＝17.2Hz,1H),2.16–1.87(m,3H),1.87–1.68(m,2H),1.46(dd,J＝31.6,8.6Hz,5H).13C NMR(101MHz,CDCl3)δ219.0,140.0,139.8,128.5,127.3,126.3,123.6,49.4,46.9,33.3,32.4,28.5,24.0,22.9.IR(KBr)νmax 2925,2853,2363,1701,1650,1541,1441,1264,754,697cm-1.HRMS(ESI)calcd for C17H21O[M+H]+:241.1587,found:m/z 241.1585.
实施例22
Figure BDA0000735928320000151
在烧瓶中加入磁子，加入A22(71mg，0.25mmol)，1,2-二氯乙烷1.5mL，加入AgNTf2(4.8mg，0.0125mmol)和HOTf(1.9mg，0.0125mmol)在室温下搅拌12小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比15:1)纯化，即可得到产物B22(49.7mg，70％)：黄色液体，1H NMR(400MHz,CDCl3)δ7.46–7.23(m,5H),6.00(d,J＝4.8Hz,1H),3.80(s,3H),3.67(s,1H),3.18(d,J＝18.0Hz,1H),2.65–2.41(m,2H),1.88(d,J＝9.2Hz,2H),1.61(t,J＝11.7Hz,2H),1.51(t,J＝12.1Hz,1H),1.29(t,J＝10.5Hz,2H).13CNMR(101MHz,CDCl3)δ209.7,173.9,139.8,139.2,128.5,127.6,126.4,124.1,59.8,52.4,51.8,36.7,34.0,29.8,27.1,26.3.IR(KBr)νmax 2932,2855,1740,1707,1493,1446,1360,1298,1269,1232,1215,1156,1105,1014,765,699cm-1.HRMS(ESI)calcd for C18H21O3[M+H]+:285.1485,found:m/z 285.1484.
实施例23
Figure BDA0000735928320000152
在烧瓶中加入磁子，加入A23(74.5mg，0.25mmol)，1,2-二氯乙烷1.5mL，加入AgNTf2(4.8mg，0.0125mmol)和HOTf(1.9mg，0.0125mmol)在室温下搅拌24小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比15:1)纯化，即可得到产物B23′(56.0mg，75％)：无色液体， 1H NMR(400MHz,CDCl3)δ7.39(t,J＝6.9Hz,2H),7.33(d,J＝6.7Hz,1H),7.24(d,J＝7.1Hz,2H),3.79(d,J＝0.9Hz,3H),2.69(s,2H),2.61(d,J＝12.0Hz,1H),2.52(dt,J＝12.9,6.2Hz,1H),2.33–2.23(m,1H),2.22–2.13(m,1H),2.11–2.02(m,1H),1.93–1.83(m,1H),1.67(ddd,J＝27.2,21.5,9.5Hz,3H),1.48(d,J＝7.2Hz,2H),1.31–1.18(m,1H).13C NMR(101MHz,CDCl3)δ203.76,173.71,147.32,140.15,136.67,128.47,127.85,127.36,77.39,77.07,76.76,57.02,52.13,37.49,29.91,28.66,28.31,27.77,27.33,25.74.IR(KBr)νmax2931,2861,1738,1685,1491,1439,1364,1340,1264,1201,1165,1123,1097,1059,764,742,701cm-1.HRMS(ESI)calcd for C19H23O3[M+H]+:299.1642,found:m/z 299.1640.
实施例24
Figure BDA0000735928320000161
在烧瓶中加入磁子，加入A24(88.5mg，0.25mmol)，1,2-二氯乙烷1.5mL，加入AgNTf2(4.8mg，0.0125mmol)和HOTf(1.9mg，0.0125mmol)在室温下搅拌10小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比15:1)纯化，即可得到产物B24(21.0mg，24％)和B24'(57.5mg，65％)，均是无色液体。若反应时间延长为24小时，则B24消失，B24'产率升高为89％。B24：1H NMR(400MHz,CDCl3)δ7.31(dd,J＝14.5,7.5Hz,3H),7.15(d,J＝7.4Hz,2H),5.73(d,J＝2.4Hz,1H),3.88(d,J＝11.0Hz,1H),3.77(s,2H),3.40(dd,J＝14.5,7.2Hz,1H),3.11(d,J＝18.5Hz,1H),2.59(dd,J＝19.5,1.7Hz,1H),2.08(t,J＝14.3Hz,1H),1.91(dt,J＝24.9,11.3Hz,3H),1.36(dd,J＝17.3,8.1Hz,11H).13C NMR(101MHz,CDCl3)δ207.40,173.01,140.96,140.39,128.07,127.86,127.07,124.95,77.33,77.02,76.70,60.15,52.11,46.53,38.44,34.75,27.39,25.90,24.84,24.53,23.79,22.31,21.69,21.55.B24'：1H NMR(400MHz,CDCl3)δ7.38(t,J＝7.3Hz,2H),7.30(dd,J＝14.1,6.8Hz,1H),7.12(d,J＝7.2Hz,2H), 3.76(s,3H),2.99–2.86(m,1H),2.80–2.69(m,1H),2.65(d,J＝12.7Hz,1H),2.51–2.40(m,1H),2.04(t,J＝11.0Hz,2H),1.97(d,J＝13.2Hz,1H),1.86(dd,J＝19.2,7.6Hz,2H),1.49(d,J＝12.2Hz,1H),1.22(ddd,J＝29.8,25.2,15.6Hz,11H),0.87(d,J＝11.4Hz,1H).13C NMR(101MHz,CDCl3)δ197.99,173.65,154.96,141.26,134.44,128.43,127.50,126.69,77.39,77.07,76.75,57.67,52.04,32.40,29.96,29.43,27.03,26.50,25.86,23.83,23.46,22.61,22.30,20.17.IR(KBr)νmax2929,2863,1738,1668,1622,1490,1467,1436,1361,1325,1247,1222,1199,1145,1090,1030,977,916,765,734,703cm-1.HRMS(ESI)calcd for C23H31O3[M+H]+:355.2268,found:m/z 355.2266.
实施例25
Figure BDA0000735928320000171
在烧瓶中加入磁子，加入A25(139.5mg，0.25mmol)，1,2-二氯乙烷1.5mL，入AgNTf2(4.8mg，0.0125mmol)和HOTf(1.9mg，0.0125mmol)在室温下搅拌24小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比15:1)纯化，即可得到产物B25(98.0mg，70％)：白色固体，熔点176～178℃，1H NMR(400MHz,CDCl3)δ7.32(ddd,J＝23.1,15.0,7.7Hz,5H),5.70(s,1H),3.81(s,3H),3.46(d,J＝18.5Hz,1H),2.99(s,1H),2.93(d,J＝13.5Hz,1H),2.71(d,J＝18.6Hz,1H),1.97(d,J＝12.1Hz,1H),1.83(d,J＝12.4Hz,1H),1.73(d,J＝13.6Hz,2H),1.59–1.42(m,5H),1.40–1.23(m,8H),1.19–1.00(m,7H),0.93(s,3H),0.91–0.86(m,3H),0.85(d,J＝6.2Hz,6H),0.76–0.65(m,2H),0.63(s,3H).13C NMR(101MHz,CDCl3)δ212.9,173.3,145.9,139.0,128.5,127.7,126.5,118.7,58.8,56.3,56.2,55.5,54.7,52.9,52.7,49.5,42.7,42.3,39.9,39.5,36.2,35.8,35.2,33.8,31.9,29.4,28.2,28.0,24.1,23.9,22.8,22.6,21.7,18.7,13.7,12.1.IR(KBr)νmax 2932,2867,2361,1739,1493,1441,1379,1300,1269,1227,1140,1090,1045,910,819,764,736,697cm-1.HRMS(ESI)calcd for C38H55O3[M+H]+:559.4146,found:m/z 559.4136.
实施例26
Figure BDA0000735928320000181
在烧瓶中加入磁子，加入A26(143mg，0.25mmol)，1,2-二氯乙烷1.5mL，加入AgNTf2(4.8mg，0.0125mmol)和HOTf(1.9mg，0.0125mmol)在80℃下搅拌30小时，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比15:1)纯化，即可得到产物B26(79.0mg，55％)：白色固体，熔点184～185℃，1H NMR(400MHz,CDCl3)δ7.30–7.22(m,2H),7.13(d,J＝7.6Hz,2H),5.66(s,1H),3.81(s,3H),3.44(d,J＝18.5Hz,1H),2.98(s,1H),2.92(d,J＝13.4Hz,1H),2.70(d,J＝18.4Hz,1H),2.34(s,3H),1.96(d,J＝12.0Hz,1H),1.81(d,J＝12.1Hz,2H),1.73(d,J＝13.5Hz,1H),1.57–1.40(m,5H),1.39–1.23(m,6H),1.23–1.03(m,6H),1.06–0.96(m,3H),0.93(s,3H),0.89–0.87(m,3H),0.85(d,J＝5.7Hz,6H),0.76–0.65(m,2H),0.63(s,3H).13C NMR(101MHz,CDCl3)δ213.2,173.4,145.7,137.5,136.0,129.2,126.4,117.8,58.8,56.3,56.2,55.6,54.6,52.8,52.7,49.5,42.7,42.3,39.8,39.5,36.1,35.8,35.2,33.8,31.9,29.4,28.2,28.0,24.1,23.9,22.8,22.6,21.7,21.1,18.7,13.7,12.1.IR(KBr)νmax 2932,2867,2362,1739,1718,1512,1441,1380,1269,1228,1140,1090,1044,804,739cm-1.HRMS(ESI)calcd for C39H57O3[M+H]+:573.4302,found:m/z 573.4290.
实施例27
Figure BDA0000735928320000182
在烧瓶中加入磁子，加入A27(144mg，0.25mmol)，1,2-二氯乙烷1.5mL，加入AgNTf2(4.8mg，0.0125mmol)和HOTf(1.9mg，0.0125mmol)在室温下搅拌24小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比15:1)纯化，即可得到产物B27(95.0mg，66％)：白色固体， 熔点188～190℃，1H NMR(400MHz,CDCl3)δ7.33(s,2H),7.01(t,J＝7.8Hz,2H),5.65(s,1H),3.81(s,3H),3.45(d,J＝18.5Hz,1H),2.98–2.84(m,2H),2.70(d,J＝18.4Hz,1H),1.97(d,J＝11.6Hz,1H),1.80(d,J＝11.2Hz,2H),1.72(d,J＝14.0Hz,1H),1.58–1.41(m,5H),1.41–1.28(m,6H),1.27–1.17(m,3H),1.15–0.99(m,6H),0.93(s,3H),0.90–0.87(m,3H),0.85(d,J＝6.1Hz,6H),0.74–0.66(m,2H),0.63(s,3H).13C NMR(101MHz,CDCl3)δ212.7,173.2,162.4(d,JC-F＝247.5Hz),144.9,135.1(d,JC-F＝3.3Hz),128.2(d,JC-F＝8.0Hz),118.7,115.4(d,JC-F＝21.3Hz),58.9,56.3,56.2,55.4,54.7,53.1,52.7,49.5,42.7,42.2,39.8,39.5,36.1,35.8,35.2,33.8,31.8,29.4,28.2,28.0,24.1,23.9,22.8,22.5,21.7,18.7,13.7,12.1. 19F NMR(376MHz,CDCl3)δ-114.49.IR(KBr)νmax2932,2867,2361,1739,1718,1600,1508,1441,1379,1269,1227,1156,1091,1044,842,813,740,650cm-1.HRMS(ESI)calcd for C38H54FO3[M+H]+:577.4052,found:m/z 577.4046.
实施例28
Figure BDA0000735928320000191
在烧瓶中加入磁子，加入A28(85mg，0.25mmol)，1,2-二氯乙烷1.5mL，加入AgNTf2(4.8mg，0.0125mmol)和HOTf(1.9mg，0.0125mmol)在室温下搅拌12小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比15:1)纯化，即可得到产物B28(53mg，65％)：淡黄色液体， 1H NMR(400MHz,CDCl3)δ7.29(d,J＝19.8Hz,5H),5.87(s,1H),3.68(s,3H),3.05(dd,J＝19.5,6.2Hz,1H),2.80(d,J＝17.9Hz,1H),2.71(d,J＝22.7Hz,1H),2.61(dd,J＝15.5,5.8Hz,1H),2.55–2.43(m,1H),2.25–2.09(m,1H),1.85–1.51(m,3H),1.48–1.20(m,4H),0.91(s,3H).13C NMR(101MHz,CDCl3)δ217.00,216.69,173.07,172.77,145.73,144.27,138.91,138.66,128.54,128.50,127.67,127.54,125.40,125.34,121.35,121.08,77.37,77.05,76.73,51.74,50.82,49.48,48.34,47.67,46.48,40.63,38.65,38.31,37.89,37.62,35.02,34.86,32.92,32.68,28.95,24.14,23.40,22.57,22.55,14.09.IR(KBr)νmax 2932,2867,1742,1494,1438,1373,1262,1174,764,695cm- 1.HRMS(ESI)calcd for C22H29O3[M+H]+:341.2138,found:m/z 341.2136.
实施例29
Figure BDA0000735928320000201
在烧瓶中加入磁子，加入A29(66.5mg，0.25mmol)，1,2-二氯乙烷1.5mL，加入AgNTf2(4.8mg，0.0125mmol)和HOTf(1.9mg，0.0125mmol)在室温下搅拌12小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比15:1)纯化，即可得到产物B29(43.2mg，65％)：淡黄色液体， 1H NMR(400MHz,CDCl3)δ7.42(d,J＝7.0Hz,2H),7.35(t,J＝7.3Hz,2H),7.29(s,1H),5.92(s,1H),3.24(s,1H),2.84(d,J＝18.1Hz,1H),2.59(d,J＝18.0Hz1H),2.20–2.03(m,1H),1.40–1.20(m,3H),1.13(s,3H),0.78(d,J＝6.4Hz,3H),0.62(d,J＝6.6Hz,3H).13C NMR(101MHz,CDCl3)δ216.4,143.2,140.3,128.5,127.3,125.4,123.8,53.9,49.4,45.1,37.4,26.5,25.3,21.1,17.3,16.6,9.4.IR(KBr)νmax2961,2925,2361,2337,1754,1651,1540,1492,1457,137,9,1261,1092,1029,800,753,695cm-1.HRMS(ESI)calcd for C19H23O[M+H]+:267.1743,found:m/z267.1741.
实施例30
Figure BDA0000735928320000202
在烧瓶中加入磁子，加入A1(56.5mg，0.25mmol)，硝基甲烷1.5mL，HOTf(37.5mg，0.25mmol)在室温下搅拌1小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比10:1)纯化。即可得到产物B1(45.2mg，80％)。
实施例31
Figure BDA0000735928320000203
在烧瓶中加入磁子，加入A1(56.5mg，0.25mmol)，甲苯1.5mL，HOTf(37.5mg，0.25mmol)在80℃下搅拌1小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比10:1)纯化，即可得到产物B1(25.4mg，45％)。
实施例32
Figure BDA0000735928320000211
在烧瓶中加入磁子，加入A1(56.5mg，0.25mmol)，1,2-二氯乙烷1.5mL，AgNTf2(1.0mg，0.0025mmol)和HOTf(0.375mg，0.0025mmol)在80℃下搅拌12小时，反应完全，旋除溶剂，用快速柱色谱法(洗脱液为石油醚：乙酸乙酯体积比10:1)纯化，即可得到产物B1(40.0mg，70％)。
实施例33～69，见表1：
Figure BDA0000735928320000212
其中，表1中0.2eq表示的是添加的量是A1的0.2摩尔当量；0.05eq表示的是添加的量是A1的0.05摩尔当量；溶剂的用量与A1的体积摩尔比为4mL：1mmol；纯化时所用的洗脱液为石油醚：乙酸乙酯体积比10:1。
表1
Figure BDA0000735928320000221
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (7)

1.一种二环[3.n.1]化合物的制备方法，其特征在于包括如下步骤：
将炔酮化合物溶解于溶剂中，加入催化剂，反应后分离纯化，得到二环[3.n.1]化合物；
所述的催化剂为Cu(OTf)2(II)、Fe(OTf)3(III)、Fe(OTf)2(II)、Bi(OTf)3、Sn(OTf)2、In(OTf)3、AgOTf、Zn(OTf)2、Yb(OTf)3(III)、FeCl3、InCl3、AgNTf2、AgSbF6、Fe(acac)3、氮杂卡宾金络合物、膦金络合物、HOTf、MsOH和TsOH中的至少一种；
所述的炔酮化合物，其结构式如下：
Figure FDA0002247531950000011
式中：R1为氢、烷基、酯基、酰基、苄基或取代的苄基；其中，所述的取代的苄基的苯环上的取代基为苯基、卤素、烷基、烷氧基、羟基、酰基和胺基中的至少一种；
R2为苯基乙烯基类、苯基乙炔基类或芳基；其中，R2上的苯环上的取代基为苯基、卤素、烷基、烷氧基、羟基、酰基和胺基中的至少一种；
R3为氢或烷基；其中，所述的烷基为C1～C50的烷基；
C1-C2…Cn为链长为n个碳的取代或非取代碳链，其中n＝2～9的自然数，所述的取代的取代基为氢、烷基、环烷基和氧原子中的至少一种；
所述的催化剂与炔酮化合物的摩尔比为0.01～1:1；
所述的反应的条件为0～120℃反应0.5h～40h；
所述的二环[3.n.1]化合物的结构式如下：
Figure FDA0002247531950000012
式中：R1为氢、烷基、酯基、酰基、苄基或取代的苄基；其中，所述的取代的苄基的苯环上的取代基为苯基、卤素、烷基、烷氧基、羟基、酰基和胺基中的至少一种；
R2为苯基乙烯基类、苯基乙炔基类或芳基；其中，R2上的苯环上的取代基为苯基、卤素、烷基、烷氧基、羟基、酰基和胺基中的至少一种；
R3为氢或烷基；其中，所述的烷基为C1～C50的烷基；
C1-C2…Cn为链长为n个碳的取代或非取代碳链，其中n＝2～9的自然数，所述的取代的取代基为氢、烷基、环烷基和氧原子中的至少一种。
2.根据权利要求1所述的制备方法，其特征在于：
所述的氮杂卡宾金络合物为IMesAuCl、IMesAuCl3、SIMesAuCl、IPrAuCl和SIPrAuCl中的至少一种。
3.根据权利要求1所述的制备方法，其特征在于：
所述的膦金络合物为Ph3PAuCl和[JohnPhosAuSbF6]MeCN中至少一种。
4.根据权利要求1所述的制备方法，其特征在于：
所述的溶剂为1,2-二氯乙烷、二氯甲烷、硝基甲烷和甲苯中的任意一种。
5.根据权利要求1所述的制备方法，其特征在于：
所述的溶剂与炔酮化合物的体积摩尔比为1～15mL:1mmol。
6.一种二环[3.n.1]化合物的制备方法，其特征在于包括如下步骤：
在烧瓶中加入磁子，加入0.25mmol的A23，1,2-二氯乙烷1.5mL，加入0.0125mmol的AgNTf2和0.0125mmol的HOTf在室温下搅拌24小时，反应完全，旋除溶剂，用快速柱色谱法纯化，即得到产物B23′；其中，所述的快速柱色谱法所用的洗脱液为石油醚：乙酸乙酯体积比15:1；
7.一种二环[3.n.1]化合物的制备方法，其特征在于包括如下步骤：
在烧瓶中加入磁子，加入0.25mmol的A24，1,2-二氯乙烷1.5mL，加入0.0125mmol的AgNTf2和0.0125mmol的HOTf在室温下搅拌10小时，反应完全，旋除溶剂，用快速柱色谱法纯化，即得到产物B24和B24'，均是无色液体；若反应时间延长为24小时，则B24消失，得到产物B24'；其中，所述的快速柱色谱法所用的洗脱液为石油醚：乙酸乙酯体积比15:1；
Figure FDA0002247531950000031
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