CN112979399B - 一种烯烃化合物的烷基-芳基化的方法及应用 - Google Patents

一种烯烃化合物的烷基-芳基化的方法及应用 Download PDF

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CN112979399B
CN112979399B CN201911215008.9A CN201911215008A CN112979399B CN 112979399 B CN112979399 B CN 112979399B CN 201911215008 A CN201911215008 A CN 201911215008A CN 112979399 B CN112979399 B CN 112979399B
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鲍红丽
朱晓韬
朱能波
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Fujian Institute of Research on the Structure of Matter of CAS
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Abstract

本申请公开了一种烯烃化合物的烷基‑芳基化的方法，包括：由包括式II所示的化合物a、式III所示的化合物b、和式Ⅳ所示的化合物c的反应体系反应制备得到式I所示的化合物I；其中，R1选自烃基、取代烃基、杂芳基、取代杂芳基中的一种；Ar选自芳基、取代芳基、杂芳基、取代杂芳基中的一种；R2选自烃基、取代烃基、杂芳基、取代杂芳基中的一种。本申请还提供了该方法的应用。本申请提供的方法采用廉价易得的催化剂，反应条件温和，绿色环保，产物的选择性和产率都较高，为有机合成领域提供了简单有效的方法来得到昂贵的烷基谐二芳基类化合物，具有广泛的研究价值和工业化应用前景。

Description

一种烯烃化合物的烷基-芳基化的方法及应用
技术领域
本申请涉及一种化合物的制备方法及其应用，具体涉及一种烯烃化合物的烷基-芳基化的方法及应用，属于有机合成领域。
背景技术
烷基谐二芳基结构是一种非常重要的结构单元，在许多重要的药物分子和天然产物中都含有烷基谐二芳基结构(如下所示有机药物分子中的谐二芳基骨架)。烯烃是广泛存在于自然界的有机小分子中，因此有必要提供一种高效的从简单烯烃出发合成类似于以下含有不对称谐二芳基结构的药物分子的方法。
Figure BDA0002299268380000011
发明内容
根据本申请的一个方面，提供了一种一种烯烃化合物的烷基-芳基化的方法，该方法具有反应原料廉价、操作简单、反应高效等优点。
所述化合物I的方法，其特征在于，由包括式II所示的化合物a、式III所示的化合物b、和式Ⅳ所示的化合物c的反应体系反应制备得到式I所示的化合物I；
Figure BDA0002299268380000021
其中，R1选自烃基、取代烃基、杂芳基、取代杂芳基中的一种；Ar选自芳基、取代芳基、杂芳基、取代杂芳基中的一种；R2选自烃基、取代烃基、杂芳基、取代杂芳基中的一种。
优选地，R1选自C1至C20的烃基、C1至C20的取代烃基、C3至C20的杂芳基、C3至C20的取代杂芳基中的一种；Ar选自C6至C20的芳基、C6至C20的取代芳基、C3至C20的杂芳基、C3至C20的取代杂芳基中的一种；R2选自C1至C20的烃基、C1至C20的取代烃基、C3至C20的杂芳基、C3至C20的取代杂芳基中的一种。
优选地，所述R1选自烷基、取代烷基中的一种；所述烷基包括直链烷基、支链烷基、环烷基。
优选地，所述R2选自芳基、取代芳基、杂芳基、取代杂芳基中的一种。
优选地，所述R1选自C1至C20的烷基、C1至C20的取代烷基中的一种；所述烷基包括直链烷基、支链烷基、环烷基；Ar选自C6至C20的芳基、C6至C20的取代芳基、C3至C20的杂芳基、C3至C20的取代杂芳基中的一种；所述R2选自C6至C20的芳基、C6至C20的取代芳基、C3至C20的杂芳基、C3至C20的取代杂芳基中的一种。
优选地，所述取代烃基、取代芳基、取代杂芳基中的取代基是非烃取代基；所述非烃取代基选自氧、卤素、腈基、具有式(1)所示结构式的基团、具有式(2)所示结构式的基团、具有式(3)所示结构式的基团中的至少一种：
Figure BDA0002299268380000031
M11选自氢、C1至C10的烃基、C1至C10的卤代烃基；
Figure BDA0002299268380000032
M21选自氢、C1至C10的烃基、C1至C10的卤代烃基；
M31-O-* 式(3)
M31选自氢、C1至C10的烃基、C1至C10的卤代烃基。
优选地，M11选自氢、C1至C10的烷基、C1至C10的氟、氯和/或溴取代烷基；M21选自氢、C1至C10的烷基、C1至C10的氟、氯和/或溴取代烷基；M31选自氢、C1至C10的烷基、C1至C10的氟、氯和/或溴取代烷基。
优选地，所述R1选自以下取代基中的一种：
Figure BDA0002299268380000033
优选地，所述Ar选自以下取代基中的一种：
Figure BDA0002299268380000041
优选地，所述R2选自以下取代基中的一种：
Figure BDA0002299268380000042
优选地，所述化合物I选自以下化合物中的至少一种：
Figure BDA0002299268380000051
Figure BDA0002299268380000061
优选地，所述反应体系中包括催化剂；所述催化剂选自CuTc、CuOAc、CuI、CuBr、CuCl、Cu(OTf)2、Cu(acac)2、Cu(CH3CN)4PF6、Cu(CH3CN)4BF4中的至少一种。
优选地，所述催化剂包括Cu(CH3CN)4PF6。
优选地，所述反应体系中包括碱；所述碱选自N,N-二异丙基乙胺、二乙基甲胺、吡啶、N-甲基吗啡啉、N,N-二乙基乙胺、氟化铯、碳酸铯、碳酸氢钠、碳酸钾、磷酸钾、氟化钾、叔丁醇钾、醋酸钠中的至少一种。
优选地，所述碱包括N,N-二异丙基乙胺。
优选地，所述反应体系中包括配体；所述配体选自以下化合物中的至少一种：
Figure BDA0002299268380000062
优选地，所述配体包括
Figure BDA0002299268380000063
优选地，所述化合物a、所述化合物b、所述化合物c和所述碱的摩尔比为：化合物a:化合物b:化合物c:碱＝1～3:2～6:1:1～3。
优选地，所述化合物a、所述化合物b、所述化合物c和所述碱的摩尔比为：化合物a:化合物b:化合物c:碱＝1.5:3:1:2。
优选地，催化剂和配体的摩尔比为：催化剂:配体＝1:1～2。
优选地，催化剂和配体的摩尔比为：催化剂:配体＝1:1.4。
优选地，所述化合物c与所述催化剂的摩尔比为：化合物c:催化剂＝10～40:1。
优选地，所述化合物c与所述催化剂的摩尔比为：化合物c:催化剂＝20:1。
可选地，所述反应体系中的溶剂选自MTBE(甲基叔丁基醚)、CH3CN(乙腈)、Et2O(乙醚)、苯甲醚、THF(四氢呋喃)、二氧六环、甲醇、乙酸乙酯和乙二醇二甲醚中的至少一种。
优选地，所述溶剂包括四氢呋喃。
优选地，所述反应的反应温度为10～30℃，反应时间为12～36小时。
根据本申请的另一个方面，提供了上述方法在制备用于抗精神病、抗乳腺癌的药物中的应用。
根据本申请的又一个方面，提供了上述方法在制备TXA2受体拮抗剂、S1P受体调节剂中的应用。
本申请中，C1～C10、C1～C20等均指基团中所包含的碳原子数。
本申请中，“烃基”是由烃类化合物分子上失去任意一个氢原子所形成的基团；所述烃类化合物包括烷烃化合物、烯烃化合物、炔烃化合物和芳烃化合物。如甲苯失去苯环上甲基对位的氢原子所形成的对甲苯基，或者甲苯失去甲基上任意一个氢原子形成的苄基等。
本申请中，“烷基”是由烷烃化合物分子上失去任意一个氢原子所形成的基团。
本申请中，所述“杂芳基”是芳香环中含有O、N、S杂原子的芳香族化合物(简称杂芳化合物)分子上失去芳香环上任意一个氢原子所形成的基团；如哌嗪环上失去任意一个氢原子所形成哌嗪基。
本申请中，所述“卤素”指氟、氯、溴、碘中的至少一种。
本申请中，所述“非烃取代基”指含有除H和C以外其他元素(如卤素、S、O、P、N等)的化合物失去任意一个氢原子所形成的基团。
本申请中，对所述“取代烃基”和“取代杂芳基”的碳原子限定，是指烃基、烷基、杂芳基本身所含的碳原子数，而非取代后的碳原子数。如C1～C10的取代烃基，指碳原子数为C1～C10的烃基上，至少一个氢原子被取代基取代。如金刚烷基上一个氢被—C≡N取代形成的含有碳原子数为11的基团。
本申请中，所述取代基为氧时，指基团中任意一个C原子上的两个H原子被O替代，形成C＝O键。
本申请中，结构式中的“Me”表示甲基，“Et”表示乙基，“Ph”表示苯基，“Ac”表示乙酸失去—OH形成的基团CH3 C(＝O)—；“Bu”和“n-Bu”均表示正丁基；“t-Bu”和“But”均表示叔丁基。
本申请中，结构式表示的化合物，包含所有的异构体。即符合结构式表达的所有异构体均包含在本申请的保护范围内。
本申请能产生的有益效果包括：
1)铜作为廉价易得的金属广泛存在于自然界中，使得铜催化剂在资源、价格以及后处理方面具有优势，有利于降低本申请提供的制造方法的工艺成本。
2)烷基羧酸是有机合成中广泛使用的廉价、无毒的物质，烷基羧酸经过很简单的处理得到的脂肪族过氧乙酰化合物可作为一种高效的烷基化试剂。本申请将烷基羧酸制得的脂肪族过氧乙酰化合物作为高烷基化试剂(化合物a)，与芳基硼酸(化合物b)在铜催化下与烯烃发生(化合物c)1,2-烷基芳基化反应的到烷基谐二芳基类化合物(化合物Ⅰ)。该反应具有原料及催化剂廉价、条件温和、操作简单、反应高效等优点。
3)利用该发明可以简单高效地合成市场在售的药物匹莫齐抗，以及多个药物分子S1P受体调节剂、抗乳腺癌(MCF-7)。
4)本申请提供了一种由烯烃经过1,2-烷基芳基化反应合成烷基谐二芳基类化合物新方法。反应底物范围广泛，条件温和，操作简单，足以满足化工、医药、材料等的广泛需求。
5)本申请提供的方法采用廉价易得的催化剂，反应条件温和，绿色环保，产物的化学选择性和产率都较高，为有机合成领域提供了简单有效的方法来得到昂贵的烷基谐二芳基类化合物，具有广泛的研究价值和工业化应用前景。
具体实施方式
下面结合实施例详述本申请，但本申请并不局限于这些实施例。
如无特别说明，本申请的实施例中的原料和催化剂均通过商业途径购买。
实施例中，核磁共振氢谱1H-NMR在布鲁克公司(Bruker)的400AVANCEⅢ型分光仪(Spectrometer)上测定，400MHz，CDCl3；碳谱13C-NMR，100MHz，CDCl3；和JEOL ECZ600S上测定氢谱1H-NMR，600Mz，CDCl3；碳谱13C-NMR，150MHz，CDCl3。
HRMS(DART)采用Thermo ISQ QD测定。
GC-MS采用Thermo Fisher Scientific LTQ FTICR-MS测定。
化合物I的产率，以烯烃化合物c的量为基准，通过以下公式计算得到：
产率％＝(目标产物实际得到的质量÷目标产物理论上应得到的质量)×100％。
实施例1
Figure BDA0002299268380000091
在氮气保护下，将六氟磷酸四乙腈铜(0.01mmol)和配体L8(0.014mmol,7.0mol％)加入25mL的反应管中，抽真空，氮气置换三次，加入四氢呋喃(1mL)，在室温下搅拌30分钟。将烯烃1-1(0.2mmol,1.0equiv)、LPO(0.3mmol,1.5equiv)、苯硼酸(0.6mmol,3equiv)和二异丙基乙胺(0.4mmol,2.0equiv)加入反应管中，室温下反应12小时，反应完毕后，乙酸乙酯稀释，硅胶快速过滤，旋转蒸发仪减压除去溶剂后，柱层析分离，得产物样品记为2-1。
2-1可为以下结构：
Figure BDA0002299268380000101
化合物检测数据如下：
Figure BDA0002299268380000102
无色液体2-1-1(59.4mg,77％产率)。1H NMR(400MHz,CDCl3)δ7.80-7.67(m,4H),7.44-7.35(m,2H),7.32(dd,J＝8.4,1.8Hz,1H),7.28-7.22(m,4H),7.17-7.11(m,1H),4.03(t,J＝7.8Hz,1H),2.20-2.04(m,2H),1.32-1.19(m,20H),0.90-0.84(m,3H)。13C NMR(100MHz,CDCl3)δ145.33,142.89,133.65,132.22,128.49,128.09,127.81,127.67,126.92,126.16,125.98,125.97,125.39,51.51,35.63,32.07,29.84,29.82,29.80,29.66,29.51,28.20,22.85,14.30。HRMS(DART)calcd for[C29H38]+(M+):386.2968,found:386.2969。
Figure BDA0002299268380000103
无色液体2-1-2(49.7mg,74％产率)。1H NMR(400MHz,CDCl3)δ7.31-7.20(m,8H),7.19-7.12(m,2H),3.88(t,J＝7.8Hz,1H),2.09-1.96(m,2H),1.33-1.19(m,20H),0.88(t,J＝6.8Hz,3H)。13C NMR(100MHz,CDCl3)δ145.38,128.36,127.87,125.98,51.39,35.74,31.95,29.67,29.52,29.38,28.05,22.73,14.17。HRMS(DART)calcd for[C25H40N]+(M+NH4 +):354.3155,found:354.3154。
Figure BDA0002299268380000111
无色液体2-1-3(47.6mg,68％产率)。1H NMR(400MHz,CDCl3)δ7.29-7.19(m,4H),7.17-7.03(m,5H),3.84(t,J＝7.8Hz,1H),2.28(s,3H),2.00(q,J＝7.8Hz,2H),1.33-1.19(m,20H),0.93-0.82(m,3H)。13C NMR(100MHz,CDCl3)δ145.68,142.41,135.42,129.08,128.36,127.83,127.74,125.91,51.01,35.83,31.97,29.71,29.69,29.54,29.40,28.09,22.74,21.01,14.17。HRMS(DART)calcd for[C26H42N]+(M+NH4 +):368.3312,found:368.3312。
Figure BDA0002299268380000112
无色液体2-1-4(43.4mg,62％产率)。1H NMR(600MHz,CDCl3)δ7.29-7.22(m,4H),7.18-7.13(m,2H),7.04(d,J＝6.3Hz,2H),6.97(d,J＝7.3Hz,1H),3.83(t,J＝7.8Hz,1H),2.30(s,3H),2.01(q,J＝7.8Hz,2H),1.32-1.22(m,20H),0.88(t,J＝7.1Hz,3H)。13C NMR(100MHz,CDCl3)δ145.50,145.33,137.83,128.70,128.33,128.22,127.86,126.76,125.92,124.81,51.38,35.77,31.94,29.69,29.66,29.51,29.37,28.07,22.71,21.54,14.14。HRMS(DART)calcd for[C26H42N]+(M+NH4 +):368.3312,found:368.3311。
Figure BDA0002299268380000113
无色液体2-1-5(35.0mg,50％产率)。1H NMR(400MHz,CDCl3)δ7.32(d,J＝7.5Hz,1H),7.27-7.08(m,8H),4.07(t,J＝7.6Hz,1H),2.26(s,3H),2.02-1.97(m,2H),1.29-1.22(m,20H),0.88(t,J＝6.9Hz,3H).13C NMR(100MHz,CDCl3)δ144.96,143.02,136.33,130.43,128.23,128.21,126.62,125.96,125.89,125.79,46.91,36.31,31.95,29.77,29.69,29.67,29.54,29.39,28.08,22.73,19.97,14.17。HRMS(EI)calcd for[C26H42N]+:368.3312,found:368.3311。
Figure BDA0002299268380000121
无色液体2-1-6(41.6mg,53％产率)。1H NMR(400MHz,CDCl3)δ7.23-7.15(m,6H),7.12-7.04(m,3H),3.77(t,J＝7.8Hz,1H),1.98-1.90(m,2H),1.24-1.13(m,29H),0.83-0.78(m,3H)。13C NMR(100MHz,CDCl3)δ147.54,144.51,141.31,127.27,126.87,126.30,124.86,124.16,49.93,34.81,33.27,30.90,30.35,28.64,28.61,28.47,28.33,27.04,21.67,13.10。HRMS(DART)calcd for[C29H48N]+(M+NH4 +):410.3781,found:410.3780。
Figure BDA0002299268380000122
无色液体2-1-7(43.0mg,59％产率)。1H NMR(600MHz,CDCl3)δ7.28-7.19(m,2H),7.17(dd,J＝7.9,1.3Hz,2H),7.18-7.08(m,1H),7.14-7.07(m,1H),6.98(d,J＝7.6Hz,1H),6.90(dd,J＝7.5,1.4Hz,1H),4.03(t,J＝7.6Hz,1H),2.31(s,3H),2.20(s,3H),1.97(q,J＝7.5Hz,2H),1.29-1.21(m,20H),0.87(t,J＝7.1Hz,3H)。13C NMR(100MHz,CDCl3)δ144.01,141.85,134.15,132.05,129.24,127.17,127.15,126.34,125.52,124.68,59.38,45.79,35.20,30.90,28.71,28.64,28.62,28.47,28.33,27.02,21.67,20.28,18.45,13.18,13.10。HRMS(DART)calcd for[C27H44N]+(M+NH4 +):382.3468,found:382.3468。
Figure BDA0002299268380000123
白色固体2-1-8(45.5mg,55％产率)。1H NMR(400MHz,CDCl3)δ7.30(t,J＝1.9Hz,1H),7.24-7.17(m,3H),7.15-7.02(m,5H),3.76(t,J＝7.8Hz,1H),1.99-1.86(m,2H),1.23-1.12(m,20H),0.84-0.78(m,3H).13C NMR(100MHz,CDCl3)δ146.78,143.42,129.85,128.89,128.09,127.47,126.77,125.50,125.25,121.47,50.09,34.51,30.89,28.63,28.61,28.60,28.58,28.54,28.43,28.32,26.88,21.67,13.10。HRMS(DART)calcd for[C25H39NBr]+(M+NH4 +):432.2260,found:432.2259。
Figure BDA0002299268380000131
白色固体2-1-9(50.5mg,61％产率)。1H NMR(400MHz,CDCl3)δ7.35-7.27(m,2H),7.23-7.16(m,2H),7.14-7.07(m,3H),7.05-7.00(m,2H),3.76(t,J＝7.8Hz,1H),1.99-1.82(m,2H),1.27-1.13(m,20H),0.81(t,J＝6.9Hz,3H)。13C NMR(100MHz,CDCl3)δ143.70,143.36,130.38,128.59,127.43,126.71,125.18,118.71,49.75,34.53,30.89,28.63,28.61,28.59,28.58,28.56,28.44,28.32,26.90,21.67,13.10。HRMS(DART)calcd for[C25H39NBr]+(M+NH4 +):432.2260,found:432.2261。
Figure BDA0002299268380000132
无色液体2-1-10(42.2mg,57％产率)。1H NMR(400MHz,CDCl3)δ7.23-7.05(m,9H),3.78(t,J＝7.8Hz,1H),1.98-1.86(m,2H),1.24-1.13(m,20H),0.85-0.77(m,3H)。13C NMR(100MHz,CDCl3)δ143.80,142.83,130.63,128.17,127.43,126.71,125.16,49.69,34.59,30.89,28.63,28.61,28.60,28.58,28.56,28.45,28.32,26.91,21.67,13.10。HRMS(EI+)calcd for[C25H35Cl]+(M+):370.2427,found:370.2424。
Figure BDA0002299268380000133
无色液体2-1-11(53.8mg,70％产率)。1H NMR(600MHz,CDCl3)δ7.30-7.25(m,4H),7.24-7.20(m,4H),7.18-7.15(m,1H),4.54(s,2H),3.88(t,J＝7.8Hz,1H),2.01(q,J＝8.5,7.6Hz,2H),1.31-1.21(m,20H),0.87(t,J＝7.0Hz,3H)。13C NMR(100MHz,CDCl3)δ145.81,144.99,135.09,128.68,128.44,128.23,127.84,126.13,51.13,46.18,35.66,31.95,29.69,29.66,29.65,29.51,29.38,28.01,22.72,14.15。HRMS(DART)calcd for[C26H41NCl]+(M+NH4 +):402.2922,found:402.2922。
Figure BDA0002299268380000141
无色液体2-1-12(45.7mg,58％产率)。1H NMR(400MHz,CDCl3)δ7.25-7.06(m,7H),6.97-6.84(m,2H),3.80(t,J＝7.8Hz,1H),2.20(s,3H),1.93(q,J＝7.9Hz,2H),1.24-1.13(m,20H),0.80(t,J＝6.8Hz,3H).13C NMR(100MHz,CDCl3)δ169.63,148.75,144.99,142.95,128.74,128.42,127.88,126.11,121.29,50.79,35.81,31.95,29.66,29.51,29.38,28.01,22.73,21.20,14.17。HRMS(DART)calcd for[C27H39O2]+(M+H+):395.2945,found:395.2944。
Figure BDA0002299268380000142
无色液体2-1-13(41.1mg,61％产率)。1H NMR(600MHz,CDCl3)δ8.55(d,J＝5.7Hz,1H),7.56-7.50(m,1H),7.34-7.31(m,2H),7.27(t,J＝6.9Hz,2H),7.19-7.12(m,2H),7.08-7.05(m,1H),4.03(t,J＝7.1Hz,1H),2.21(dq,J＝14.8,7.2Hz,1H),2.05(dq,J＝15.5,7.7Hz,1H),1.30-1.20(m,20H),0.86(t,J＝6.6Hz,3H)。13C NMR(100MHz,CDCl3)δ164.22,149.20,144.00,136.33,128.41,128.04,126.28,122.59,121.15，53.85,35.10,31.93,29.68,29.65,29.62,29.51,29.36,27.97,22.71,14.14。HRMS(DART)calcd for[C24H36N]+(M+H+):338.2842,found:338.2842。
Figure BDA0002299268380000143
无色液体2-1-14(47.8mg,58％产率)。1H NMR(400MHz,CDCl3)δ8.16-8.09(m,1H),7.85-7.79(m,1H),7.71(dd,J＝7.3,2.4Hz,1H),7.49-7.39(m,4H),7.30-7.20(m,4H),7.15-7.10(m,1H),4.70(t,J＝7.6Hz,1H),2.23-2.05(m,2H),1.36-1.20(m,20H),0.90-0.84(m,3H)。13C NMR(100MHz,CDCl3)δ145.29,140.72,134.08,132.02,128.85,128.36,128.11,126.84,125.99,125.87,125.44,125.28,124.31,123.75,46.33,36.52,31.98,29.82,29.72,29.70,29.58,29.41,28.28,22.76,14.20。HRMS(DART)calcd for[C29H38]+(M+):386.2968,found:386.2968。
Figure BDA0002299268380000151
无色液体2-1-15(27.0mg,43％产率,异构体比＝2.8:1,通过GC-MS测定)。1H NMR(400MHz,CDCl3)δ7.27-7.22(m,2H),7.19-7.11(m,3H),3.43-3.35(m,2H),2.18-2.02(m,2H),1.81-1.67(m,3H),1.57-1.49(m,2H),1.42-1.23(m,21H),0.88(t,J＝6.7Hz,3H)。13CNMR(100MHz,CDCl3)δ141.14,141.02,130.58,128.52,128.40,128.39,128.22,128.21,128.19,126.52,126.21,125.62,125.53,40.25,39.75,36.01,34.67,34.64,31.95,31.55,29.88,29.75,29.72,29.70,29.69,29.61,29.54,29.38,29.36,28.73,28.26,22.71,18.64,18.52,18.43,18.12,14.14。HRMS(DART)calcd for[C23H42N]+(M+NH4 +):332.3312,found:332.3310。
Figure BDA0002299268380000152
白色固体2-1-16(55.3mg,54％产率)。1H NMR(400MHz,CDCl3)δ7.22-7.15(m,4H),7.13-7.06(m,2H),6.98-6.93(m,1H),6.88(t,J＝2.6Hz，1H),3.74(t,J＝7.8Hz,1H),2.84-2.73(m,2H),2.42(dd,J＝18.8,8.5Hz,1H),2.35-2.27(m,1H),2.24-2.16(m,1H),2.11-2.01(m,1H),1.98-1.83(m,5H),1.55-1.38(m,6H),1.23-1.15(m,20H),0.82-0.78(m,6H)。13C NMR(100MHz,CDCl3)δ205.90，144.42，141.87，136.26，135.25，127.34，127.32,126.81，124.88，124.27，124.09，50.01，49.99，49.51，46.98，43.28，37.13，34.84，34.76，30.90，30.59，29.89，28.65，28.62，28.45，28.33，27.04，25.56，24.62，21.67，20.56，13.10，12.83。HRMS(DART)calcd for[C37H53O]+(M+H+):513.4091,found:513.4090。
Figure BDA0002299268380000161
白色固体2-1-17(59.2mg,55％产率)。1H NMR(400MHz,CDCl3)δ7.29-7.22(m,4H),7.21-7.12(m,2H),7.04-6.99(m,1H),6.95-6.92(m,1H),3.80(t,J＝7.8Hz,1H),2.85-2.77(m,2H),2.60(s,1H),2.39-2.29(m,2H),2.26-2.17(m,1H),2.08-1.95(m,4H),1.90-1.85(m,1H),1.77-1.61(m,4H),1.51-1.38(m,4H),1.29-1.21(m,20H),0.88-0.85(m,6H)。13CNMR(100MHz,CDCl3)δ145.53,142.66,137.81,136.49,128.35,127.88,125.90,125.34,125.01,124.94,87.56,79.89,74.04,51.06,49.60,47.14,43.87,39.22,38.99,35.84,32.80,31.95,30.95,29.70,29.67,29.50,29.38,28.10，27.31,26.14，22.83,22.72,14.15,12.71。HRMS(DART)calcd for[C39H58ON]+(M+NH4 +):556.4513,found:556.4510。
实施例2
Figure BDA0002299268380000162
在氮气保护下，将六氟磷酸四乙腈铜(0.01mmol)和配体L8(0.014mmol,7.0mol％)加入25mL的反应管中，抽真空，氮气置换三次，加入四氢呋喃(1mL)，在室温下搅拌30分钟。将烯烃2-乙烯基萘(0.2mmol,1.0equiv)、烷基过氧酰1-2(0.3mmol,1.5equiv)、苯硼酸(0.6mmol,3equiv)和二异丙基乙胺(0.4mmol,2.0equiv)加入反应管中，室温下反应12小时，反应完毕后，乙酸乙酯稀释，硅胶快速过滤，旋转蒸发仪减压除去溶剂后，柱层析分离，得产物样品记为2-2。
2-2可为以下结构：
Figure BDA0002299268380000171
化合物检测数据如下：
Figure BDA0002299268380000172
无色液体2-2-1(44.2mg,67％产率)。1H NMR(400MHz,CDCl3)δ7.82-7.69(m,4H),7.48-7.39(m,2H),7.36-7.32(m,1H),7.29-7.25(m,4H),7.20-7.13(m,1H),4.05(t,J＝7.8Hz,1H),2.18-2.07(m,2H),1.33-1.24(m,12H),0.88-0.83(m,3H)。13C NMR(100MHz,CDCl3)δ145.24,142.79,133.52,132.09,128.39,127.98,127.70,127.56,126.83,126.06,125.88,125.86,125.29,51.39,35.51,31.88,29.71,29.49,29.33,28.07,22.68,14.14。HRMS(DART)calcd for[C25H34N]+(M+NH4 +):348.2686,found:348.2685。
Figure BDA0002299268380000181
无色液体2-2-2(44.1mg,73％产率)。1H NMR(400MHz,CDCl3)δ7.82-7.67(m,4H),7.47-7.37(m,2H),7.33(dd,J＝8.5,1.9Hz,1H),7.30-7.23(m,4H),7.20-7.11(m,1H),4.05(t,J＝7.8Hz,1H),2.21-2.06(m,2H),1.35-1.23(m,8H)，0.89-0.81(m,3H)。13C NMR(100MHz,CDCl3)δ145.24,142.80,133.55,132.12,128.39,127.99,127.71,127.56,126.83,126.06,125.88,125.86,125.29,51.41,35.53,31.75,29.37,28.05,22.67,14.09。HRMS(DART)calcd for[C23H26]+(M+):302.2029,found:302.2029。
Figure BDA0002299268380000182
无色液体2-2-3(43.5mg,72％产率)。1H NMR(400MHz，CDCl3)δ7.81-7.68(m,4H)，7.47-7.37(m，2H)，7.33(dd，J＝8.5，1.9Hz，1H)，7.29-7.22(m，4H)，7.19-7.12(m，1H)，4.05(t，J＝7.7Hz，1H)，2.21-2.01(m，2H),1.52-1.44(m,1H),1.31-1.22(m,4H),0.82(d,J＝6.6Hz,6H)。13C NMR(100MHz,CDCl3)δ145.24,142.80,133.56,132.13,128.40,128.00,127.72,127.57,126.83,126.07,125.88,125.87,125.30,51.42,39.01,35.74,27.81,25.84,22.66,22.64。HRMS(DART)calcd for[C23H26]+(M+):302.2029,found:302.2029。
Figure BDA0002299268380000183
无色液体2-2-4(44.2mg,70％产率,dr＝1:1)。1H NMR(400MHz,CDCl3)δ7.82-7.67(m,4H),7.47-7.37(m,2H),7.34(dd,J＝8.6,1.8Hz,1H),7.31-7.23(m,4H),7.20-7.12(m,1H)，4.01(t，J＝7.8Hz，1H)，2.25-2.03(m，2H)，1.42-1.28(m,5H)，1.19-1.05(m,2H)，0.86(d，J＝6.5Hz,3H)，0.81(t,J＝7.3Hz,3H)。13C NMR(100MHz,CDCl3)δ145.33,145.20,142.88,142.73,133.55,132.11,128.40,128.01,128.00,127.94,127.71,127.56,126.79,126.07,125.93,125.88,125.82,125.29,51.79,34.96,34.54,33.01,29.33,29.30,19.23,11.38。
Figure BDA0002299268380000191
无色液体2-2-5(47.5mg,69％产率,dr＝1:1)。1H NMR(400MHz,CDCl3)δ7.81-7.67(m,4H),7.47-7.37(m,2H),7.36-7.31(m,1H),7.30-7.23(m,4H),7.19-7.11(m,1H),4.00(t,J＝7.8Hz,1H),2.25-2.02(m,2H),1.56-1.46(m,1H),1.34-1.23(m,1H),1.21-1.09(m,2H),1.04-0.96(m,1H),0.91(dd,J＝6.7,1.3Hz,3H),0.84(s,9H)。13C NMR(100MHz,CDCl3)δ145.31,145.20,142.86,142.76,133.59,132.17,132.15,128.44,128.43,128.06,128.04,127.98,127.74,127.59,126.82,126.79,126.11,126.10,126.00,125.91,125.85,125.32,51.77,51.21,51.18,37.87,33.17,31.09,30.07,29.40,22.69,22.67。HRMS(DART)calcdfor[C26H32]+(M+):344.2499,found:344.2498。
Figure BDA0002299268380000192
无色液体2-2-6(37.4mg,57％产率)。1H NMR(400MHz,CDCl3)δ7.80-7.67(m,4H),7.45-7.36(m,2H),7.33(dd,J＝8.6,1.8Hz,1H),7.30-7.23(m,4H),7.18-7.11(m,1H),4.05(t,J＝7.8Hz,1H),2.20-2.07(m,J＝7.0Hz,2H),1.71-1.65(m,2H),1.57-1.43(m,4H),1.38-1.25(m,5H),1.07-0.95(m,2H)。13C NMR(100MHz,CDCl3)δ145.29,142.85,133.61,132.18,128.44,128.04,127.76,127.61,126.88,126.11,125.92,125.34,51.43,40.01,36.25,35.79,32.78,27.23,25.22。HRMS(DART)calcd for[C25H28]+(M+):328.2186,found:328.2185。
Figure BDA0002299268380000201
无色液体2-2-7(39.3mg,65％产率)。1H NMR(400MHz,CDCl3)δ7.83-7.67(m,4H),7.48-7.38(m,2H),7.35(dd,J＝8.6,1.8Hz,1H),7.31-7.24(m,4H),7.20-7.13(m,1H),3.97(t,J＝7.7Hz,1H),2.17-2.05(m,2H),1.20(t,J＝8.4Hz,2H),0.87(s,9H)。13C NMR(100MHz,CDCl3)δ145.28,142.79,133.54,132.11,128.43,128.05,127.94,127.71,127.57,126.73,126.09,125.90,125.88,125.32,52.26,42.47,30.56,30.38,29.40。HRMS(DART)calcd for[C23H30N]+(M+NH4 +):320.2373,found:320.2373。
Figure BDA0002299268380000202
无色液体2-2-8(47.9mg,63％产率)。1H NMR(400MHz,CDCl3)δ7.82-7.67(m,4H),7.47-7.37(m,2H),7.33(dd,J＝8.4,1.8Hz,1H),7.30-7.24(m,4H),7.20-7.12(m,1H),3.94(t,J＝7.7Hz,1H),2.18-2.01(m,2H),1.96-1.87(m,3H),1.73-1.64(m,3H),1.63-1.56(m,3H),1.46(d,J＝2.9Hz,6H),1.08(t,J＝8.5Hz,2H)。13C NMR(100MHz,CDCl3)δ145.35,142.85,133.58,132.13,128.41,128.02,127.97,127.73,127.57,126.78,126.06,125.92,125.88,125.29,52.25,42.93,42.45,37.28,32.32,28.77,28.49。HRMS(DART)calcd for[C29H32]+(M+):380.2499,found:380.2498。
Figure BDA0002299268380000203
无色液体2-2-9(48.4mg,72％产率)。1H NMR(400MHz,CDCl3)δ7.80-7.69(m，3H)，7.67-7.64(m，1H),7.46-7.36(m,2H)，7.30(dd,J＝8.6,1.8Hz,1H),7.27-7.23(m,5H),7.22-7.20(m,1H),7.18-7.09(m,4H)，4.07(t,J＝7.8Hz,1H),2.65(t,J＝7.6Hz,2H),2.29-2.05(m,2H),1.71-1.56(m,2H)。13C NMR(100MHz,CDCl3)δ144.98,142.49,142.33,133.56,132.18,128.47，128.31,128.09,128.00,127.75,127.59,126.80,126.18,125.95,125.90,125.75,125.39,51.32,35.92,35.03,29.82。HRMS(DART)calcd for[C26H24]+(M+):336.1873,found:336.1873。
Figure BDA0002299268380000211
无色液体2-2-10(46.8mg,76％产率)。1H NMR(400MHz,CDCl3)δ7.82-7.66(m,4H),7.48-7.37(m,2H),7.32(dd,J＝8.5,1.9Hz,1H),7.27(d,J＝4.3Hz,4H),7.20-7.12(m,1H),4.05(t,J＝7.8Hz,1H),3.47(t,J＝6.7Hz,2H),2.24-2.06(m,2H),1.78-1.67(m,2H),1.55-1.44(m,2H),1.37-1.29(m,2H)。13C NMR(100MHz,CDCl3)δ144.96,142.51,133.55,132.17,128.48,128.10,127.96,127.72,127.59,126.72,126.20,125.98,125.87,125.40,51.29,45.09,35.32,32.49,27.36,26.92。HRMS(DART)calcd for[C22H23Cl]+(M+):322.1483,found:322.1480。
Figure BDA0002299268380000212
无色液体2-2-11(51.4mg,73％产率)。1H NMR(400MHz,CDCl3)δ7.85-7.66(m,4H),7.49-7.36(m,2H),7.32(dd,J＝8.5,1.9Hz,1H),7.27(d,J＝4.5Hz,4H),7.21-7.13(m,1H),4.05(t,J＝7.8Hz,1H),3.35(t,J＝6.8Hz,2H),2.25-2.08(m,2H),1.99-1.82(m,2H),1.49-1.37(m,2H)。13C NMR(100MHz,CDCl3)δ144.73,142.25,133.54,132.19,128.52,128.16,127.93,127.73,127.59,126.66,126.28,126.01,125.87,125.45,51.23,34.61,33.55,32.85,26.73。HRMS(DART)calcd for[C21H21Br]+(M+):352.0821,found:352.0819。
Figure BDA0002299268380000213
无色液体2-2-12(29.9mg,42％产率)。1H NMR(400MHz,CDCl3)δ7.81-7.69(m,4H),7.47-7.38(m,2H),7.33(dd,J＝8.5,1.9Hz,1H),7.30-7.24(m,4H),7.20-7.13(m,1H),5.88-5.73(m,1H),5.03-4.89(m,2H),4.04(t,J＝7.8Hz,1H),2.22-2.07(m,2H),2.05-1.97(m,2H),1.37-1.22(m,12H)。13C NMR(100MHz,CDCl3)δ145.24,142.78,139.27,133.54,132.11,128.41,128.01,128.00,127.71,127.58,126.83,126.08,125.90,125.87,125.32,114.13,51.40,35.51,33.84,29.69,29.48,29.13,28.93,28.08。HRMS(DART)calcd for[C27H32]+(M+):356.2499,found:356.2499。
Figure BDA0002299268380000221
无色液体2-2-13(28.7mg,46％产率)。1H NMR(400MHz,CDCl3)δ7.83-7.67(m,4H),7.48-7.37(m,2H),7.33(dd,J＝8.5,1.9Hz,1H),7.30-7.24(m,4H),7.20-7.12(m,1H),4.05(t,J＝7.8Hz,1H),2.22-2.10(m,4H),1.92(t,J＝2.6Hz,1H),1.53-1.41(m,4H),1.36-1.29(m,2H)。13C NMR(100MHz,CDCl3)δ145.06,142.61,133.54,132.14,128.43,128.04,127.97,127.70,127.57,126.76,126.13,125.92,125.86,125.34,84.64,68.18,51.32,35.34,28.74,28.31,27.55,18.38。HRMS(DART)calcd for[C24H24]+(M+):312.1873,found:312.1872。
Figure BDA0002299268380000222
无色液体2-2-14(47.7mg，69％产率)。1H NMR(400MHz,CDCl3)δ7.83-7.65(m,4H),7.47-7.37(m,2H),7.35-7.30(m,1H),7.29-7.23(m,4H)，7.20-7.11(m,1H)，4.04(t,J＝7.8Hz,1H),3.63(s，3H),2.26(t，J＝7.5Hz,2H),2.20-2.08(m,2H),1.62-1.53(m,2H),1.40-1.27(m,4H)。13C NMR(100MHz,CDCl3)δ174.23,145.02,142.59,133.54,132.14,128.43,128.05,127.96,127.71,127.57,126.75,126.14,125.93,125.85,125.35,51.47,51.33,35.27,34.05,29.16,27.71,24.82。HRMS(DART)calcd for[C24H30O2N]+(M+NH4 +):364.2271,found:364.2271。
Figure BDA0002299268380000231
无色液体2-2-15(38.9mg,62％产率)。1H NMR(600MHz,CDCl3)δ7.79(dd,J＝13.1,7.7Hz,2H),7.74(d,J＝8.5Hz,1H),7.70(s,1H),7.47-7.39(m,2H),7.35(dd,J＝8.5,1.8Hz,1H),7.30-7.25(m,4H),7.19-7.14(m,1H),4.24(t,J＝7.9Hz,1H),2.10-1.96(m,2H),1.86-1.76(m,2H),1.69-1.63(m,2H),1.59(d,J＝3.5Hz，1H),1.23-1.17(m,1H),1.15-1.11(m,2H),1.11-1.06(m,1H),1.02-0.94(m,2H)。13C NMR(100MHz,CDCl3)δ145.35,142.85,133.55,132.09,128.41,128.00,127.73,127.57,126.89,126.03,125.88,125.86,125.30,47.98,43.40,34.88,33.58,33.39,26.66,26.17。HRMS(DART)calcd for[C24H26]+(M+):314.2029,found:314.2029。
实施例3
Figure BDA0002299268380000232
在氮气保护下，将六氟磷酸四乙腈铜(0.01mmol)和配体L8(0.014mmol,7.0mol％)加入25mL的反应管中，抽真空，氮气置换三次，加入四氢呋喃(1mL)，在室温下搅拌30分钟。将烯烃2-乙烯基萘(0.2mmol,1.0equiv)、LPO(0.3mmol,1.5equiv)、芳基硼酸1-3(0.6mmol,3equiv)和二异丙基乙胺(0.4mmol,2.0equiv)加入反应管中，室温下反应12小时，反应完毕后，乙酸乙酯稀释，硅胶快速过滤，旋转蒸发仪减压除去溶剂后，柱层析分离，得产物样品记为3-2。
3-2可为以下结构(aDMF(0.5mL)作碱反应24小时)：
Figure BDA0002299268380000241
化合物检测数据如下：
Figure BDA0002299268380000242
白色固体2-3-1(64.8mg,81％产率)。1H NMR(400MHz,CDCl3)δ7.83-7.65(m,4H),7.45-7.29(m,3H),7.22-7.12(m,1H),7.11-7.05(m,2H),7.00-6.92(m,1H),4.09-3.90(m,1H),2.28(s,3H),2.15-2.05(m,2H)，1.33-1.19(m,20H),0.91-0.82(m,3H)。13C NMR(100MHz,CDCl3)δ145.30,143.01,137.95,133.67,132.23,128.93,128.36,128.07,127.81,127.66,126.95,125.95,125.93,125.34,125.04,51.49，35.64，32.06，29.84，29.81，29.79，29.65，29.50，28.21,22.84,21.64,14.27。HRMS(DART)calcd for[C30H40]+(M+):400.3125,found:400.3125。
Figure BDA0002299268380000243
白色固体2-3-2(44.2mg,51％产率)。1H NMR(400MHz,CDCl3)δ7.78-7.66(m,3H),7.62-7.59(m,1H),7.43-7.33(m,2H),7.29(dd,J＝8.4,1.8Hz,1H),7.26-7.22(m,1H),7.04-6.98(m,1H),6.95-6.91(m,1H),4.19(t,J＝7.6Hz,1H),2.27(s,3H),2.25(s,3H),2.12-2.00(m,2H),1.33-1.21(m,20H),0.91-0.83(m,3H)。13C NMR(100MHz，CDCl3)δ142.78，139.97，136.27，135.42,133.57，132.10，131.43，127.92，127.74，127.60，127.16，126.83，126.76,126.25,125.84,125.24,46.82,36.30,32.04,29.90,29.78,29.76,29.73,29.64,29.47,28.22,22.81,21.00,19.98,14.24。HRMS(DART)calcd for[C31H42]+(M+):414.3281,found:414.3285。
Figure BDA0002299268380000251
白色固体2-3-3(45.5mg,55％产率).1H NMR(400MHz,CDCl3)δ7.82-7.65(m,4H),7.45-7.30(m,3H),7.08-6.98(m,3H),3.97(t,J＝7.8Hz,1H),2.20(s,3H),2.19(s,3H),2.14-2.02(m,2H),1.32-1.20(m,20H),0.91-0.82(m,3H).13C NMR(100MHz,CDCl3)δ143.16,142.76,136.44,134.19,133.59,132.11,129.64,129.39,127.97,127.72,127.56,126.85,125.80,125.77,125.19,51.04,35.60,31.96,29.74,29.71,29.68,29.54,29.39,28.14,22.73,19.92,19.34,14.16.HRMS(DART)calcd for[C31H42]+(M+):414.3281,found:414.3280。
Figure BDA0002299268380000252
白色固体2-3-4(46.9mg,58％产率)。1H NMR(400MHz,CDCl3)δ7.81-7.70(m,3H),7.69-7.64(m,1H),7.47-7.38(m,2H),7.29(dd,J＝8.5,1.9Hz,1H),7.24-7.19(m,2H),6.98-6.91(m,2H),4.02(t,J＝7.8Hz,1H),2.20-1.99(m,2H),1.33-1.20(m,20H),0.92-0.84(m,3H)。13C NMR(100MHz,CDCl3)δ161.29(d,J＝244.3Hz),142.59,140.92(d,J＝3.3Hz),133.54,132.15,129.33(d,J＝8.1Hz),128.10,127.63,127.59,126.65,125.99,129.79,125.42,115.14(d,J＝21.3Hz),50.61,35.65,31.95,29.69,29.66,29.65,29.53,29.38,28.02,22.72,14.15。HRMS(DART)calcd for[C29H37F]+(M+):404.2874,found:404.2874。
Figure BDA0002299268380000261
白色固体2-3-5(59.6mg,71％产率)。1H NMR(400MHz,CDCl3)δ7.83-7.71(m,3H),7.67(d,J＝2.0Hz,1H),7.49-7.39(m,2H),7.30-7.18(m,5H),4.02(t,J＝7.8Hz,1H),2.18-2.01(m,2H),1.29-1.21(m,20H),0.87(t,J＝6.8Hz,3H)。13C NMR(100MHz,CDCl3)δ143.72,142.23,133.49,132.14,131.75,129.34,128.50,128.15,127.69,127.59,126.60,126.03,125.82,125.47,50.72,35.42,31.94,29.73,29.68,29.65,29.51,29.38,27.99,22.72,14.16。HRMS(DART)calcd for[C29H41NCl]+(M+NH4 +):438.2922,found:438.2920。
Figure BDA0002299268380000262
白色固体2-3-6(40.5mg,48％产率)。1H NMR(400MHz,CDCl3)δ7.82-7.73(m,3H),7.69(d,J＝1.8Hz,1H),7.49-7.39(m,2H),7.33(dd,J＝8.6,2.0Hz,1H),7.29-7.21(m,1H),6.85-6.70(m,2H),4.37(t,J＝7.8Hz,1H),2.19-2.01(m,2H),1.35-1.18(m,20H),0.87(t,J＝6.9Hz,3H)。13C NMR(100MHz,CDCl3)δ160.95(dd,J＝246.9,81.45Hz),141.28,133.47,132.18,129.27(dd,J＝9.5,6.2Hz),129.09(dd,J＝14.9,3.8Hz),128.08,127.72,127.58,126.62,126.02,125.98,125.50,111.12(dd,J＝20.6,3.7Hz),103.74(dd,J＝26.9,25.3Hz),43.04,34.69,31.94,29.68,29.66,29.65,29.62,29.58,29.50,29.38,27.86,22.72,14.16。HRMS(DART)calcd for[C29H36F2]+(M+):422.2780,found:422.2780。
Figure BDA0002299268380000271
白色固体2-3-7(58.4mg,67％产率)。1H NMR(600MHz,CDCl3)δ7.86-7.73(m,8H),7.50-7.36(m,6H),4.27-4.20(m,1H),2.29-2.20(m,2H),1.40-1.24(m,20H),0.90(t,J＝7.1Hz,3H)。13C NMR(100MHz,CDCl3)δ142.66,133.54,132.14,128.02,127.75,127.59,126.98,125.98,125.93,125.36,51.40,35.31,31.96,29.76,29.70,29.68,29.56,29.39,28.12,22.74,14.19。HRMS(EI+)calcd for[C33H44]+(M+):436.3130,found:436.3135。
Figure BDA0002299268380000272
白色固体2-3-8(46.2mg,50％产率)。1H NMR(600MHz,CDCl3)δ7.83-7.72(m,4H),7.57-7.49(m,4H),7.47-7.34(m,7H),7.32-7.29(m,1H),4.10(t,J＝7.7Hz,1H),2.22-2.11(m,2H),1.36-1.23(m,20H),0.87(t,J＝6.9Hz,3H)。13C NMR(100MHz,CDCl3)δ144.40,142.68,140.97,138.94,133.56,132.15,128.70,128.37,128.08,127.72,127.59,127.14,127.04,127.01,126.80,125.94,125.92,125.35,51.08,35.54,31.95,29.73,29.70,29.68,29.55,29.39,28.11,22.73,14.18。HRMS(EI+)calcd for[C35H42]+(M+):462.3287,found:462.3296。
实施例4
Figure BDA0002299268380000273
在氮气保护下，将六氟磷酸四乙腈铜(0.01mmol)和配体L8(0.014mmol,7.0mol％)加入25mL的反应管中，抽真空，氮气置换三次，加入四氢呋喃(1mL)，在室温下搅拌30分钟。将烯烃4-氟苯乙烯(0.2mmol,1.0equiv)、3-氯丙酰(0.6mmol,3.0equiv)、4-氟苯硼酸(1.0mmol,5equiv)和二异丙基乙胺(0.2mmol,1.0equiv)加入反应管中，室温下反应36小时，反应完毕后，乙酸乙酯稀释，硅胶快速过滤，旋转蒸发仪减压除去溶剂后，柱层析分离，得产物样品记为2-4，产率为56％。
Figure BDA0002299268380000281
1H NMR(400MHz,CDCl3)δ7.21-7.11(m,4H),7.02-6.92(m,4H),3.88(t,J＝7.9Hz,1H),3.53(t,J＝6.5Hz,2H),2.20-2.07(m,2H),1.77-1.63(m,2H)。13C NMR(100MHz,CDCl3)δ161.42(d,J＝244.7Hz),140.03(d,J＝3.3Hz),129.07(d,J＝8.1Hz),115.41(d,J＝20.9Hz),49.14,44.92,33.08,30.89。19F NMR(376MHz,CDCl3)δ-116.68。
实施例5
Figure BDA0002299268380000282
在氮气保护下，将六氟磷酸四乙腈铜(0.01mmol)和配体L8(0.014mmol,7.0mol％)加入25mL的反应管中，抽真空，氮气置换三次，加入四氢呋喃(1mL)，在室温下搅拌30分钟。将烯烃3-氯苯乙烯(0.2mmol,1.0equiv)、4-溴丁酰(0.6mmol,3.0equiv)、3,4-二甲基苯硼酸(1.0mmol,5equiv)和二异丙基乙胺(0.2mmol,1.0equiv)加入反应管中，室温下反应36小时，反应完毕后，乙酸乙酯稀释，硅胶快速过滤，旋转蒸发仪减压除去溶剂后，柱层析分离，得产物样品记为2-5，产率为45％。
Figure BDA0002299268380000291
1H NMR(600MHz,CDCl3)δ7.21-7.16(m,2H),7.14-7.08(m,2H),7.06-7.03(m,1H),6.97-6.91(m,2H),3.82-3.74(m,1H),3.35(t,J＝6.9Hz,2H),2.21(s,3H),2.20(s,3H),2.03-1.97(m,2H),1.87(dt,J＝14.5,7.0Hz,2H)，1.43-1.32(m,2H)。13C NMR(150MHz,CDCl3)δ147.44,141.50,136.83,134.79,134.28,129.91,129.79,129.17,127.90,126.35,126.03,124.98,50.65,34.74,33.59,32.81,26.69,20.01,19.43。
实施例6
Figure BDA0002299268380000292
取DMAP(0.12mmol),30％双氧水(1.5mmol)和环己基甲酸(1.2mmol)溶于二氯甲烷(1.5mL)冷却至零下15摄氏度搅拌10分钟，然后再加入DCC(1.32mmol)。保持温度在零下10摄氏度到零下15摄氏度条件下搅拌3小时。然后用15mL正己烷/二氯甲烷＝10:1的溶液抽滤，旋转蒸发仪减压除去溶剂后得到环己基乙酰。
在氮气保护下，将六氟磷酸四乙腈铜(0.01mmol)和配体L8(0.014mmol,7.0mol％)加入25mL的反应管中，抽真空，氮气置换三次，加入四氢呋喃(1mL)，在室温下搅拌30分钟。将烯烃2-乙烯基萘(0.2mmol,1.0equiv)、上述抽滤得到的过氧酰、2-噻吩硼酸(1.0mmol,5equiv)和二异丙基乙胺(0.2mmol,1.0equiv)加入反应管中，室温下反应36小时，反应完毕后，乙酸乙酯稀释，硅胶快速过滤，旋转蒸发仪减压除去溶剂后，柱层析分离，得产物样品记为2-6，产率为55％。
Figure BDA0002299268380000301
1H NMR(600MHz,CDCl3)δ7.78-7.68(m,3H),7.63(s,1H),7.41-7.29(m,3H),7.06(d,J＝6.2Hz,1H),6.84(dd,J＝5.1,3.5Hz,1H),6.80-6.72(m,1H),4.38(t,J＝7.8Hz,1H),2.02-1.93(m,2H),1.78(d,J＝13.0Hz,1H),1.68-1.52(m,4H),1.15-1.09(m,1H),1.08-1.00(m,3H),0.95-0.86(m,2H)。13C NMR(150MHz,CDCl3)δ149.98,142.28,133.50,132.30,128.19,127.74,127.59,126.51,126.13,125.98,125.92,125.43,123.71,123.39,44.92,43.65,34.88,33.64,32.92,26.55,26.08。
实施例7
Figure BDA0002299268380000302
在氮气保护下，将Cu(acac)2(0.005mmol)和配体L7(0.005mmol)加入25mL的反应管中，抽真空，氮气置换三次，加入甲基叔丁基醚(1mL)，在室温下搅拌30分钟。将烯烃4-氟苯乙烯(0.2mmol,1.0equiv)、3-氯丙酰(0.2mmol,1.0equiv)、4-氟苯硼酸(0.4mmol,2equiv)和NaOAc(0.2mmol,1.0equiv)加入反应管中，10℃下反应36小时，反应完毕后，乙酸乙酯稀释，硅胶快速过滤，旋转蒸发仪减压除去溶剂后，柱层析分离，得产物样品记为2-7，产率为56％。
Figure BDA0002299268380000303
1H NMR(400MHz,CDCl3)δ7.21-7.11(m,4H),7.02-6.92(m,4H),3.88(t,J＝7.9Hz,1H),3.53(t,J＝6.5Hz,2H),2.20-2.07(m,2H),1.77-1.63(m,2H)。13C NMR(100MHz,CDCl3)δ161.42(d,J＝244.7Hz),140.03(d，J＝3.3Hz),129.07(d,J＝8.1Hz),115.41(d,J＝20.9Hz),49.14,44.92,33.08,30.89。19F NMR(376MHz,CDCl3)δ-116.68。
实施例8
Figure BDA0002299268380000311
在氮气保护下，将Cu(OTf)2(0.02mmol)和配体L3(0.04mmol)加入25mL的反应管中，抽真空，氮气置换三次，加入乙腈(1mL)，在室温下搅拌30分钟。将烯烃4-氟苯乙烯(0.2mmol,1.0equiv)、3-氯丙酰(0.6mmol,3.0equiv)、4-氟苯硼酸(1.2mmol,6equiv)和Et2NMe(0.6mmol,3.0equiv)加入反应管中，30℃下反应24小时，反应完毕后，乙酸乙酯稀释，硅胶快速过滤，旋转蒸发仪减压除去溶剂后，柱层析分离，得产物样品记为2-8，产率为22％。
Figure BDA0002299268380000312
1H NMR(400MHz,CDCl3)δ7.21-7.11(m,4H),7.02-6.92(m,4H),3.88(t,J＝7.9Hz,1H)，3.53(t，J＝6.5Hz，2H),2.20-2.07(m,2H),1.77-1.63(m,2H)。13C NMR(100MHz,CDCl3)δ161.42(d,J＝244.7Hz),140.03(d,J＝3.3Hz),129.07(d,J＝8.1Hz),115.41(d,J＝20.9Hz),49.14,44.92,33.08,30.89。19F NMR(376MHz,CDCl3)δ-116.68。
本发明提出的一种烯烃的1,2-烷基芳基化合成烷基谐二芳基类化合物反应已通过相关实施例进行了相关描述，这些实施例并非限制本发明的保护范围，只是通过具体实施更好的阐述本发明的方法高效、简单、环境友好、试用范围广等特点。
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。

Claims (15)

1.一种烯烃化合物的烷基-芳基化的方法，其特征在于，包括：
由包括式II所示的化合物a、式III所示的化合物b、和式Ⅳ所示的化合物c的反应体系反应制备得到式I所示的化合物I；
Figure FDA0003646250830000011
式II 式III 式Ⅳ 式I
其中，R1选自C1至C20的烃基、C1至C20的取代烃基、C3至C20的杂芳基、C3至C20的取代杂芳基中的一种；
Ar选自C6至C20的芳基、C6至C20的取代芳基、C3至C20的杂芳基、C3至C20的取代杂芳基中的一种；
R2选自C1至C20的烃基、C1至C20的取代烃基、C3至C20的杂芳基、C3至C20的取代杂芳基中的一种；
所述反应体系中包括催化剂；
所述催化剂选自Cu(OTf)2、Cu(acac)2、Cu(CH3CN)4PF6中的至少一种；
所述反应体系中包括碱；所述碱选自N,N-二异丙基乙胺、二乙基甲胺、醋酸钠中的至少一种；
所述反应体系中包括配体；所述配体选自以下化合物中的至少一种：
Figure FDA0003646250830000012
2.根据权利要求1所述的方法，其特征在于，所述R1选自C1至C20的烷基、C1至C20的取代烷基中的一种；所述烷基包括直链烷基、支链烷基、环烷基；
Ar选自C6至C20的芳基、C6至C20的取代芳基、C3至C20的杂芳基、C3至C20的取代杂芳基中的一种；
所述R2选自C6至C20的芳基、C6至C20的取代芳基、C3至C20的杂芳基、C3至C20的取代杂芳基中的一种。
3.根据权利要求1所述的方法，其特征在于，所述取代烃基、取代芳基、取代杂芳基中的取代基是非烃取代基；
所述非烃取代基选自氧、卤素、腈基、具有式(1)所示结构式的基团、具有式(2)所示结构式的基团、具有式(3)所示结构式的基团中的至少一种：
Figure FDA0003646250830000021
M11选自氢、C1至C10的烃基、C1至C10的卤代烃基；
Figure FDA0003646250830000022
M21选自氢、C1至C10的烃基、C1至C10的卤代烃基；
M31-O-*式(3)
M31选自氢、C1至C10的烃基、C1至C10的卤代烃基。
4.根据权利要求3所述的方法，其特征在于，M11选自氢、C1至C10的烷基、C1至C10的氟、氯和/或溴取代烷基；
M21选自氢、C1至C10的烷基、C1至C10的氟、氯和/或溴取代烷基；
M31选自氢、C1至C10的烷基、C1至C10的氟、氯和/或溴取代烷基。
5.根据权利要求1所述的方法，其特征在于，所述R1选自以下取代基中的一种：
Figure FDA0003646250830000031
所述Ar选自以下取代基中的一种：
Figure FDA0003646250830000032
所述R2选自以下取代基中的一种：
Figure FDA0003646250830000041
所述化合物I选自以下化合物中的至少一种：
Figure FDA0003646250830000042
Figure FDA0003646250830000051
6.根据权利要求1所述的方法，其特征在于，所述催化剂包括Cu(CH3CN)4PF6。
7.根据权利要求1所述的方法，其特征在于，所述碱包括N,N-二异丙基乙胺。
8.根据权利要求1所述的方法，其特征在于，所述配体包括：
Figure FDA0003646250830000061
9.根据权利要求1所述的方法，其特征在于，所述化合物a、所述化合物b、所述化合物c和所述碱的摩尔比为：
化合物a:化合物b:化合物c:碱＝1～3:2～6:1:1～3。
10.根据权利要求1所述的方法，其特征在于，所述化合物a、所述化合物b、所述化合物c和所述碱的摩尔比为：
化合物a:化合物b:化合物c:碱＝1.5:3:1:2。
11.根据权利要求1所述的方法，其特征在于，催化剂和配体的摩尔比为：催化剂:配体＝1:1～2。
12.根据权利要求1所述的方法，其特征在于，催化剂和配体的摩尔比为：催化剂:配体＝1:1.4。
13.根据权利要求1所述的方法，其特征在于，所述化合物c与所述催化剂的摩尔比为：化合物c:催化剂＝10～40:1。
14.根据权利要求1所述的方法，其特征在于，所述化合物c与所述催化剂的摩尔比为：化合物c:催化剂＝20:1。
15.根据权利要求1所述的方法，其特征在于，所述反应体系中的溶剂包括甲基叔丁基醚、乙腈、乙醚、苯甲醚、四氢呋喃、二氧六环、甲醇、乙酸乙酯和乙二醇二甲醚中的至少一种；
所述反应的反应温度为10～30℃，反应时间为12～36小时。
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