CN115057882A - 一类多取代烯基锡试剂及其立体选择性制备与应用 - Google Patents

一类多取代烯基锡试剂及其立体选择性制备与应用 Download PDF

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CN115057882A
CN115057882A CN202210428872.2A CN202210428872A CN115057882A CN 115057882 A CN115057882 A CN 115057882A CN 202210428872 A CN202210428872 A CN 202210428872A CN 115057882 A CN115057882 A CN 115057882A
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李�杰
胡颖
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Abstract

本发明提供了一类多取代烯基锡试剂及其立体选择性制备与应用。其中，本发明所述多取代烯基锡试剂的结构通式：
Figure DDA0003610972670000011
其中，R1、R2独立的选自酯基、氰基、芳基、芳基杂环、烷基、H、内酰胺、烯基、杂环、药物分子或天然产物，R3选自酯基、酰胺或H。本发明通过多环芳烃催化的锂化反应，实现锡试剂的定量转化，再通过转金属化和无机盐活化完成锡试剂的制备进而完成烯基锡试剂的合成。所述多取代烯基锡试剂在Stille偶联反应中应用。

Description

一类多取代烯基锡试剂及其立体选择性制备与应用
技术领域
本发明属于合成有机化学技术领域，尤其是指一类多取代烯基锡试剂及其立体选择性制备与应用。
背景技术
碳锡键作为一种十分重要的碳-金属键，被广泛应用于有机化学，生物化学，药物化学领域中。现有的传统有机锡试剂，如锡锂试剂，锡钠试剂，锡镁试剂等，普遍存在着转化率低，副产物毒性高，锡原料消耗大等缺点。随着多环芳烃催化锂化反应的发展，锡试剂能够完成定量转化，且相比于传统有机锡试剂，也更加稳定，活性更高。基于上述原因，提高有机锡试剂的转化率以及反应活性是发展新型有机锡试剂需要解决的问题，同时对于锡试剂化学选择性的调控也是一项新的研究发展方向。本发明通过筛选不同转金属化锡试剂以及阴离子从而实现对有机锡试剂的化学性质的调控，实现对反应活性的提高以及立体选择性的控制。
发明内容
为解决上述技术问题，本发明提供了一类烯基锡试剂及其立体选择性制备与应用。
本发明的第一个目的在于提供一种多取代烯基锡试剂，所述多取代烯基锡试剂的结构通式：
Figure RE-GDA0003804199300000011
其中，R1、R2独立的选自酯基、氰基、芳基、芳基杂环、烷基、H、内酰胺、烯基、杂环、药物分子或天然产物， R3选自酯基、酰胺或H。
在本发明的一个实施例中，所述多取代烯基锡试剂选自以下化合物之一：
Figure RE-GDA0003804199300000021
Figure RE-GDA0003804199300000022
Figure RE-GDA0003804199300000031
其中，R4为H、OMe或NMe2；
R5为F、Cl或OMe；
R6为Me或TBS。
本发明的第二个目的在于提供所述的多取代烯基锡试剂的制备方法，包括以下步骤：在有机溶剂中，将
Figure RE-GDA0003804199300000032
与有机锡锌试剂在催化剂作用下混合反应得到所述多取代烯基锡试剂，其中，R1、R2独立的选自酯基、氰基、芳基、芳基杂环、烷基、H、内酰胺、烯基、杂环、药物分子或天然产物， R3选自酯基、酰胺或H。
在本发明的一个实施例中，所述
Figure RE-GDA0003804199300000033
与有机锡锌试剂的用量比为摩尔比为1:1-1:3。
在本发明的一个实施例中，混合反应的条件：反应温度为-20℃至23℃，反应时间为1min-10h。
在本发明的一个实施例中，所述有机锡锌试剂的结构式： (nBu)3Sn-MX·LiCI,其中MX为金属或金属盐；其中，金属为Li、Zn、Al；金属盐为LiCl、MgBr、ZnCl或ZnOPiv，其中，ZnOPiv结构式为
Figure RE-GDA0003804199300000041
在本发明的一个实施例中，所述催化剂选自Co、Fe、Cr、Ni和Cu中的一种或多种。
在本发明的一个实施例中，所述有机溶剂选自乙腈、四氢呋喃、N,N- 二甲基甲酰胺、N,N-二甲基乙酰胺、1,4-二氧六环和N-甲基吡咯烷酮中的一种或多种。
在本发明的一个实施例中，所述有机锡锌试剂通过以下方法制备得到：
(1)，在惰性氛围中，将萘和锂碎屑混合加入有机溶剂中，混合反应；
(2)，向步骤(1)中反应液加入烷基取代的氯化锡，混合反应；
(3)，向步骤(2)中反应液加入金属盐溶液或金属，搅拌混合反应，即得所述催化剂有机锡锌试剂。
在本发明的一个实施例中，所述萘、锂碎屑和三丁基氯化锡的摩尔比为 0.05-0.2：6：2。
在本发明的一个实施例中，步骤(1)中，所述锂碎屑大小为1-5mm。
在本发明的一个实施例中，步骤(1)中，反应条件：反应时间0.5-5h，反应温度为0-40℃。
在本发明的一个实施例中，步骤(2)中，反应条件：反应时间0.5-5h，反应温度为0-40℃。
在本发明的一个实施例中，步骤(2)中，所述烷基取代的氯化锡中烷基是指三甲基、乙基或三丁基。
在本发明的一个实施例中，步骤(3)中，反应条件：反应时间0.5-5h，反应温度为0-40℃。
在本发明的一个实施例中，步骤(3)中，所述金属盐溶液中金属盐选自ZnCl2、ZnBr2、ZnI2、LiCl、MgBr和ZnOPiv中的一种或多种，所述金属选自Li、Al和Zn中的一种或多种。
本发明的第三个目的在于提供所述多取代烯基锡试剂在Stille偶联反应中应用。
本发明的上述技术方案相比现有技术具有以下优点：
本发明所述的烯基锡试剂的设计与制备方法是首次报道，且在反应性和立体选择性方面都通过无机盐活化实现了正向调控，为有机化学，生物化学，药物化学等领域提供了一类用途广泛的合成子，具有良好的应用潜力以及发展前景。本发明通过多环芳烃催化的锂化反应，实现锡试剂的定量转化，再通过转金属化和无机盐活化完成锡试剂的制备进而完成烯基锡试剂的合成。一方面，本发明制备的烯基锡试剂在空气中稳定且能大量制备，其作为有机化学，生物化学，药物化学中一类用途广泛的合成子，具有商品化价值；另一方面，本发明通过不同金属的转金属化以及无机盐活化实现对锡试剂反应活性的调控，高选择性制备烯基锡试剂。例如，在本发明中通过过渡金属催化的碳氧键活化反应中所表现出的高立体选择性和高反应活性制备烯基锡试剂。
附图说明
为了使本发明的内容更容易被清楚的理解，下面根据本发明的具体实施例并结合附图，对本发明作进一步详细的说明，其中
图1是本发明实施例1和实施例2新型锡锌试剂的制备与应用。
图2是本发明实施例1和实施例2固体锡锌试剂制备的两种方法。
图3是本发明固体锡锌试剂的反应性。
图4是本发明应用例中锡锌试剂的反应性考察结果。
图5是本发明烯基锡试剂在Migita-Kosugi-Stille反应中的合成应用实例。
具体实施方式
下面结合附图和具体实施例对本发明作进一步说明，以使本领域的技术人员可以更好地理解本发明并能予以实施，但所举实施例不作为对本发明的限定。
实施例
1，催化剂(nBu)3Sn-ZnCl·LiCl的合成
在50mL干燥和充满惰性气体(N2)的双颈圆底烧瓶中加入萘(26mg， 0.2mmol)、锂碎屑(84mg，12mmol)和干燥的THF(8.0mL)，于室温下搅拌1小时至变成深绿色溶液。称取三丁基氯化锡(4mmol，1.3g)并滴加至圆底烧瓶中，反应混合液在23℃下持续反应3小时。根据Kofron的方法，用碘滴定锡锂试剂并计算浓度，按照锡锂试剂浓度的2倍加入ZnCl2溶液，并将反应混合物在室温搅拌15分钟。使用Knochel方法滴定锡锌试剂(通常形成约0.25M溶液)，真空下除去溶剂残留即可得到相应的锡锌试剂(收率57％)。具体反应过程如图2，锡锌试剂的反应产物如图3所示。
2，烯基锡试剂化合物的合成
将1中所得(nBu)3Sn-ZnCl·LiCI与
Figure RE-GDA0003804199300000061
反应混合，得到
Figure RE-GDA0003804199300000062
具体反应条件见图4，R1，R2代表的就是不同取代基，R1选自烷基、芳基、酯基、H，R1选自烯基、烷基、芳基，R3选自酯基、酰胺、H。反应所得产物见图4，由图4可知，使用本发明所得锡锌试剂在过渡金属钴氮氧键活化中的应用，产物具有较高的收率，得到的产物为化合物8-化合物42(其核磁如下所述)。
化合物8-化合物42的核磁表征数据：
Ethyl 3-(tributylstannyl)-1H-indene-2-carboxylate(8)
The general procedure TP4 was followed using 5a(0.25mmol)and 3a(0.325mmol)at-20℃for 15min.Purification by column chromatography(PE)yielded 8(79mg,66％)as a colorless oil.(根据一般程序TP4的步骤，将5a(0.25mmol) 和3a(0.325mmol)混合，在-20℃搅拌反应十五分钟。利用柱层析法分离得到无色油状产物8(79mg,66％)。1H-NMR(400MHz,CDCl3):δ＝7.64(dd,J＝ 5.8,2.7Hz,1H),7.51(dd,J＝5.3,2.7Hz,1H),7.36–7.27(m,2H),4.30(q,J＝ 7.1Hz,2H),3.81–3.65(m,2H),1.52(ddd,J＝11.0,8.1,3.7Hz,6H),1.39–1.29 (m,9H),1.24–1.10(m,6H),0.87(t,J＝7.3Hz,9H).13C-NMR(100MHz, CDCl3):δ＝166.6,161.8,149.9,145.8,144.9,127.0,126.7,125.2,124.0,60.6, 40.9,29.3,27.6,14.6,13.8,11.5.HR-MS(EI)m/z calcd for C24H38O2Sn[M+H+]479.1967,found479.1970.
Ethyl 1-(tributylstannyl)-3,4-dihydronaphthalene-2-carboxylate(9)
The generalprocedure TP5 was followedusing 5b(0.25mmol)and3a(0.325mmol)at 0℃for 15min.Purification by column chromatography(PE)yielded 9(86mg,70％)as a colorless oil.(根据一般程序TP5的步骤，将5b(0.25mmol) 和3a(0.325mmol)混合，在0℃搅拌反应十五分钟。利用柱层析法分离得到无色油状产物9(86mg,70％)。1H-NMR(400MHz,CDCl3):δ＝7.20(dt,J＝3.8, 2.2Hz,2H),7.19–7.12(m,2H),4.25(q,J＝7.1Hz,2H),2.78–2.62(m,2H), 2.59–2.41(m,2H),1.51–1.41(m,6H),1.34–1.24(m,9H),1.06–0.93(m,6H), 0.85(t,J＝7.3Hz,9H).13C-NMR(100MHz,CDCl3):δ＝168.8,159.2,139.9, 139.2,137.2,130.4,128.0,127.2,126.2,61.1,29.4,29.0,27.6,24.1,14.5,13.9, 13.4.HR-MS(EI)m/z calcd forC25H40O2Sn[M+H+]493.2123,found493.2125.
Ethyl 9-(tributylstannyl)-6,7-dihydro-5H-benzo[7]annulene-8-carboxylate (10)
The general procedure TP5 was followed using 5c(0.25mmol)and 3a(0.325mmol)at 0℃for 50min.Purification by column chromatography(petroleum ether/EtOAc 50:1)yielded 10(60mg,47％)as a colorless oil.(根据一般程序TP5 的步骤，将5c(0.25mmol)和3a(0.325mmol)混合，在0℃搅拌反应五十分钟。利用柱层析法分离得到无色油状产物10(60mg,47％)。1H-NMR(400MHz, CDCl3):δ＝7.22(td,J＝7.3,1.9Hz,1H),7.17–7.09(m,2H),6.92(d,J＝7.4Hz, 1H),4.26(q,J＝7.1Hz,2H),2.45(t,J＝6.6Hz,2H),2.13–2.05(m,2H),1.34 (m,10H),1.22(dq,J＝14.5,7.1Hz,7H),0.97–0.84(m,6H),0.82(t,J＝7.3Hz, 9H).13C-NMR(100MHz,CDCl3):δ＝169.3,164.8,143.8,140.6,138.4,128.8,128.4,126.6,125.6,61.0,34.3,31.5,29.3,27.6,26.5,14.5,13.8,12.5.HR-MS(EI) m/zcalcd for C26H42O2Sn[M+H+]507.2280,found 507.2285.
Ethyl 4-(tributylstannyl)-2H-chromene-3-carboxylate(11)
The general procedure TP5 was followed using 5d(0.25mmol)and 3a(0.325mmol)at 0℃for 1h.Purification by column chromatography(PE)yielded 11(71 mg,58％)as a colorless oil.(根据一般程序TP5的步骤，将5d(0.25mmol)和 3a(0.325mmol)混合，在0℃搅拌反应一小时。利用柱层析法分离得到产物无色油状产物11(71mg,58％))。1H-NMR(400MHz,CDCl3):δ＝7.28–7.24(m, 1H),7.19(td,J＝7.8,1.5Hz,1H),7.04–6.88(m,2H),4.81–4.72(m,2H),4.27 (q,J＝7.1Hz,2H),1.54–1.39(m,6H),1.32(ddd,J＝19.1,7.1,5.6Hz,9H),1.13 –0.97(m,6H),0.86(t,J＝7.3Hz,9H).13C-NMR(100MHz,CDCl3):δ＝166.4, 156.2,154.4,133.9,131.1,130.5,128.7,121.6,116.4,64.6,61.2,29.3,27.5,14.5, 13.8,13.4.HR-MS(EI)m/z calcd for C24H38O3Sn[M+H+]495.1916,found 495.1918.
Ethyl 2-(tributylstannyl)cyclopent-1-ene-1-carboxylate(12)
The general procedure TP5 was followed using 5e(0.25mmol)and 3a(0.325mmol)at 0℃for 20min.Purification by column chromatography(PE)yielded 12(92mg,85％)as a colorless oil.(根据一般程序TP5的步骤，将5e(0.25mmol) 和3a(0.325mmol)混合，在0℃搅拌反应二十分钟。利用柱层析法分离得到无色油状产物12(92mg,85％))。1H-NMR(400MHz,CDCl3):δ＝4.19(q,J＝ 7.1Hz,2H),2.61(t,J＝7.5Hz,4H),1.98–1.82(m,2H),1.60–1.42(m,6H), 1.42–1.18(m,9H),1.00–0.93(m,6H),0.88(t,J＝7.3Hz,9H).13C-NMR(100 MHz,CDCl3):δ＝166.7,166.1,143.9,60.2,41.8,33.6,29.4,27.5,24.6,14.8,13.8, 10.6.HR-MS(EI)m/z calcd forC20H38O2Sn[M+H+]431.1967,found431.1969.
Methyl 2-(tributylstannyl)cyclohept-1-ene-1-carboxylate(13)
The general procedure TP5 was followed using 5f(0.25mmol)and 3a(0.325mmol)at 0℃for 30min.Purification by column chromatography(PE)yielded 13(67mg,60％)as a colorless oil.(根据一般程序TP5的步骤，将5f(0.25mmol) 和3a(0.325mmol)混合，在0℃搅拌反应三十分钟。利用柱层析法分离得到无色油状产物13(67mg,60％))。1H-NMR(400MHz,CDCl3):δ＝3.71(s,3H), 2.70–2.60(m,2H),2.60–2.40(m,2H),1.80(dt,J＝11.9,6.0Hz,2H),1.53– 1.37(m,10H),1.29(dd,J＝14.7,7.3Hz,6H),0.98–0.81(m,15H).13C-NMR (100MHz,CDCl3):δ＝170.1,169.9,144.3,52.0,35.3,32.8,29.4,28.8,27.6,26.4, 25.0,13.9,11.7.HR-MS(EI)m/z calcd for C21H40O2Sn[M+H+]445.2123,found 445.2125.
Ethyl(Z)-3-phenyl-3-(tributylstannyl)acrylate(14)
The general procedure TP4 was followed using 5g(0.25mmol)and 3a(0.325mmol)at-20℃for 15min.Purification by column chromatography(PE)yielded 14(73mg,63％)as a colorless oil.(根据一般程序TP4的步骤，将5g(0.25mmol) 和3a(0.325mmol)混合，在-20℃搅拌反应十五分钟。利用柱层析法分离得到无色油状产物14(73mg,63％))。1H-NMR(400MHz,CDCl3):δ＝7.38–7.25 (m,2H),7.26–7.18(m,1H),7.09–7.00(m,2H),6.67–6.30(m,1H),4.24(q,J ＝7.1Hz,2H),1.48–1.35(m,6H),1.33–1.21(m,9H),0.97–0.92(m,6H),0.83 (t,J＝7.3Hz,9H).13C-NMR(100MHz,CDCl3):δ＝173.8,167.9,145.9,130.8, 128.2,126.8,126.3,60.6,29.2,27.5,14.5,13.8,12.1.HR-MS(EI)m/zcalcd for C23H38O2Sn[M+H+]467.1967,found 467.1971.
Ethyl(Z)-3-(4-methoxyphenyl)-3-(tributylstannyl)acrylate(15)
The general procedure TP4 was followed using 5h(0.25mmol)and 3a(0.325mmol)at-20℃for 15min.Purification by column chromatography(PE)yielded 15(73mg,59％)as a colorless oil.(根据一般程序TP4的步骤，将5h(0.25mmol) 和3a(0.325mmol)混合，在-20℃搅拌反应十五分钟。利用柱层析法分离得到无色油状产物15(73mg,59％))。1H-NMR(400MHz,CDCl3):δ＝7.06–6.98 (m,2H),6.89–6.82(m,2H),6.46(s,1H),4.23(q,J＝7.1Hz,2H),3.81(s,3H), 1.51–1.34(m,6H),1.33–1.20(m,9H),1.04–0.88(m,6H),0.84(t,J＝7.3Hz, 9H).13C-NMR(100MHz,CDCl3):δ＝173.1,168.1,159.1,138.3,129.9,127.9, 113.7,60.5,55.5,29.2,27.5,14.5,13.8,12.2.HR-MS(EI)m/z calcd forC24H40O3Sn[M+H+]497.2072,found497.2075.
Ethyl(Z)-3-[4-(dimethylamino)phenyl]-3-(tributylstannyl)acrylate(16)
The general procedure TP4 was followed using 5i(0.25mmol)and 3a(0.325mmol)at 23℃for 4.5h.Purification by column chromatography(petroleum ether/EtOAc 50:1)yielded 16(89mg,70％)as a yellow oil.(根据一般程序TP4 的步骤，将5i(0.25mmol)和3a(0.325mmol)混合，在23℃搅拌反应四个小时三十分钟。利用柱层析法分离得到无色油状产物16(89mg,70％))。1H-NMR(400MHz,CDCl3):δ＝7.10–7.00(m,2H),6.68(d,J＝8.9Hz,2H), 6.47(s,1H),4.22(q,J＝7.1Hz,2H),2.96(s,6H),1.52–1.38(m,6H),1.36–1.20(m,9H),1.00–0.94(m,6H),0.84(t,J＝7.3Hz,9H).13C-NMR(100MHz, CDCl3):δ＝173.3,168.3,150.1,133.5,128.2,128.0,112.1,60.3,40.6,29.3,27.5, 14.5,13.9,12.4.HR-MS(EI)m/z calcd for C25H43NO2Sn[M+H+]510.2389,found 510.2394.
Ethyl(Z)-3-(4-fluorophenyl)-3-(tributylstannyl)acrylate(17)
The general procedure TP4 was followed using 5j(0.25mmol)and 3a(0.325mmol)at-20℃for 15min.Purification by column chromatography(PE)yielded 17(94mg,78％)as a colorless oil.(根据一般程序TP4的步骤，将5j(0.25mmol) 和3a(0.325mmol)混合，在-20℃搅拌反应十五分钟。利用柱层析法分离得到无色油状产物17(94mg,78％)。1H-NMR(400MHz,CDCl3):δ＝7.05–6.97 (m,4H),6.45(s,1H),4.24(q,J＝7.1Hz,2H),1.51–1.35(m,6H),1.35–1.16(m, 9H),0.98–0.92(m,6H),0.84(t,J＝7.3Hz,9H).13C-NMR(100MHz,CDCl3):δ＝172.7,167.8,162.1(d,1JC-F＝245.8Hz),141.9(d,4JC-F＝3.4Hz),131.0,128.0 (d,3JC-F＝7.9Hz),115.1(d,2JC-F＝21.4Hz),60.7,29.2,27.5,14.5,13.8,12.1. 19F-NMR(376MHz,CDCl3):δ＝-115.94(d,J＝6.0Hz).HR-MS(EI)m/z calcd forC23H37FO2Sn[M+H+]485.1872,found 485.1875.
Ethyl(Z)-3-(4-chlorophenyl)-3-(tributylstannyl)acrylate(18)
The general procedure TP4 was followed using 5k(0.25mmol)and 3a(0.325mmol)at-20℃for 15min.Purification by column chromatography(PE)yielded 18(85mg,68％)as a colorless oil.(根据一般程序TP4的步骤，将5k(0.25mmol) 和3a(0.325mmol)混合，在-20℃搅拌反应十五分钟。利用柱层析法分离得到无色油状产物18(85mg,68％)。1H-NMR(400MHz,CDCl3):δ＝7.31–7.26 (m,2H),6.99–6.94(m,2H),6.45(s,1H),4.24(q,J＝7.1Hz,2H),1.45–1.34(m, 6H),1.33–1.19(m,9H),0.97–0.92(m,6H),0.84(t,J＝7.3Hz,9H).13C-NMR (100MHz,CDCl3):δ＝172.5,167.7,144.4,132.8,131.2,128.4,127.6,60.8,29.2, 27.5,14.5,13.8,12.1.HR-MS(EI)m/z calcd for C23H37ClO2Sn[M+H+]501.1577, found 501.1581.
Ethyl(Z)-3-(3,4-dichlorophenyl)-3-(tributylstannyl)acrylate(19)
The general procedure TP4 was followed using 5l(0.25mmol)and 3a(0.325mmol)at-20℃for 15min.Purification by column chromatography(PE)yielded 19(104mg,78％)as a colorless oil.(根据一般程序TP4的步骤，将5l (0.25mmol)和3a(0.325mmol)混合，在-20℃搅拌反应十五分钟。利用柱层析法分离得到无色油状产物19(104mg,78％)。1H-NMR(400MHz,CDCl3):δ＝7.38(d,J＝8.2Hz,1H),7.13(d,J＝2.1Hz,1H),6.91–6.83(m,1H),6.45(s, 1H),4.24(q,J＝7.1Hz,2H),1.46–1.34(m,6H),1.34–1.20(m,9H),0.97– 0.92(m,6H),0.85(t,J＝7.3Hz,9H).13C-NMR(100MHz,CDCl3):δ＝171.1,167.5,146.1,132.3,131.8,130.7,130.1,128.0,125.8,60.9,29.2,27.5,14.4,13.8,12.2.HR-MS(EI)m/z calcd for C23H36Cl2O2Sn[M+H+]535.1187,found 535.1191.
Ethyl(Z)-3-(3-bromo-4-fluorophenyl)-3-(tributylstannyl)acrylate(20)
The general procedure TP4 was followed using 5m(0.25mmol)and 3a(0.325mmol)at-20℃for 15min.Purification by column chromatography(PE)yielded 20(93mg,66％)as a colorless oil.(根据一般程序TP4的步骤，将5m (0.25mmol)和3a(0.325mmol)混合，在-20℃搅拌反应十五分钟。利用柱层析法分离得到无色油状产物20(93mg,66％)。1H-NMR(400MHz,CDCl3):δ＝7.10–6.98(m,3H),6.45(s,1H),4.24(q,J＝7.1Hz,2H),1.51–1.35(m,6H), 1.35–1.18(m,9H),0.94(m,6H),0.84(td,J＝7.3,4.1Hz,9H).13C-NMR(100 MHz,CDCl3):δ＝172.6,167.8,162.1(d,1JC-F＝245.8Hz),141.9(d,4JC-F＝3.0 Hz),131.8,131.1(d,3JC-F＝6.2Hz),128.0(d,3JC-F＝7.9Hz),116.2(d,2JC-F＝22.7Hz),115.1(d,2JC-F＝21.4Hz),60.7,29.2,27.5,14.5,13.8,12.1.19F-NMR (376MHz,CDCl3):δ＝-116.04(s).HR-MS(EI)m/z calcd for C23H36BrFO2Sn [M+H+]563.0977,found563.0979.
Ethyl(Z)-3-(4-iodophenyl)-3-(tributylstannyl)acrylate(21)
The general procedure TP4 was followed using 5n(0.25mmol)and 3a(0.275mmol)at-20℃for 10min.Purification by column chromatography(PE)yielded 21(71mg,49％)as a colorless oil.(根据一般程序TP4的步骤，将5n(0.25mmol) 和3a(0.325mmol)混合，在-20℃搅拌反应十分钟。利用柱层析法分离得到无色油状产物21(71mg,49％).1H-NMR(400MHz,CDCl3):δ＝7.76–7.50(m, 2H),6.90–6.67(m,2H),6.56–6.29(m,1H),4.23(q,J＝7.1Hz,2H),1.44– 1.33(m,6H),1.33–1.18(m,9H),0.96–0.91(m,6H),0.84(t,J＝7.3Hz,9H). 13C-NMR(100MHz,CDCl3):δ＝172.5,167.7,145.6,137.3,131.1,128.2,92.2, 60.8,29.2,27.5,14.5,13.8,12.1.HR-MS(EI)m/z calcd for C23H37IO2Sn[M+H+] 593.0933,found 593.0938.
Ethyl(Z)-3-(tributylstannyl)-3-[4-(trifluoromethyl)phenyl]acrylate(22)
The general procedure TP5 was followed using 5o(0.25mmol)and 3a(0.325mmol)at-20℃for 2.5h.Purification by column chromatography(PE)yielded 22(71mg,53％)as a colorless oil.(根据一般程序TP5的步骤，将5o(0.25mmol) 和3a(0.325mmol)混合，在-20℃搅拌反应二小时三十分钟。利用柱层析法分离得到无色油状产物22(71mg,53％)。1H-NMR(400MHz,CDCl3):δ＝7.57 (d,J＝8.1Hz,2H),7.12(d,J＝8.1Hz,2H),6.46(s,1H),4.25(q,J＝7.1Hz,2H), 1.45–1.34(m,6H),1.25(m,9H),0.97–0.91(m,6H),0.83(t,J＝7.3Hz,9H). 13C-NMR(100MHz,CDCl3):δ＝172.4,167.6,149.9,131.7,128.8(q,2JC-F＝32.4 Hz),126.4,125.2(q,3JC-F＝3.7Hz),124.4(d,1JC-F＝271.8Hz),60.9,29.2,27.5, 14.5,13.8,12.1.19F-NMR(376MHz,CDCl3):δ＝-62.39(s).HR-MS(EI)m/zcalcd for C24H37F3O2Sn[M+H+]535.1840,found 535.1845.
Ethyl(Z)-4-[3-ethoxy-3-oxo-1-(tributylstannyl)prop-1-en-1-yl]benzoate(23)
The general procedure TP4 was followed using 5p(0.25mmol)and 3a(0.325mmol)at-20℃for 15min.Purification by column chromatography(petroleum ether/EtOAc 50:1)yielded 23(88mg,66％)as a colorless oil.(根据一般程序TP4 的步骤，将5p(0.25mmol)和3a(0.325mmol)混合，在-20℃搅拌反应十五分钟。利用柱层析法分离得到无色油状产物23(88mg,66％)。1H-NMR(400 MHz,CDCl3):δ＝8.07–7.96(m,2H),7.10–7.03(m,2H),6.46(s,1H),4.38(q, J＝7.1Hz,2H),4.25(q,J＝7.1Hz,2H),1.43–1.36(m,6H),1.36–1.16(m, 12H),0.97–0.92(m,6H),0.83(t,J＝7.3Hz,9H).13C-NMR(100MHz,CDCl3): δ＝172.9,167.6,166.6,151.0,131.3,129.6,128.7,126.1,61.1,60.8,29.2,27.4, 14.5,14.5,13.8,12.1.HR-MS(EI)m/z calcd for C26H42O4Sn[M+H+]539.2178, found 539.2181.
Ethyl(Z)-3-(4-cyanophenyl)-3-(tributylstannyl)acrylate(24)
The general procedure TP4 was followed using 5q(0.25mmol)and 3a(0.325mmol)at-20℃for 15min.Purification by column chromatography(petroleum ether/EtOAc 50:1)yielded 24(84mg,68％)as a colorless oil.(根据一般程序TP4 的步骤，将5q(0.25mmol)和3a(0.325mmol)混合，在-20℃搅拌反应十五分钟。利用柱层析法分离得到无色油状产物24(84mg,68％)。1H-NMR(400 MHz,CDCl3):δ＝7.61(d,J＝8.4Hz,2H),7.15–7.06(m,2H),6.44(s,1H),4.25 (q,J＝7.1Hz,2H),1.40–1.33(m,6H),1.33–1.18(m,10H),0.95–0.91(m,5H), 0.84(t,J＝7.3Hz,9H).13C-NMR(100MHz,CDCl3):δ＝172.0,167.4,151.2, 132.1,131.9,126.8,119.1,110.2,61.0,29.1,27.4,14.4,13.8,12.1.HR-MS(EI)m/z calcd for C24H37NO2Sn[M+H+]492.1919,found492.1921.
Ethyl(Z)-3-[4-(pent-4-en-1-yloxy)phenyl]-3-(tributylstannyl)acrylate(25)
The general procedure TP4 was followed using 5r(0.25mmol)and 3a(0.325mmol)at-20℃for 15min.Purification by column chromatography(PE)yielded 25(98mg,71％)as a colorless oil.(根据一般程序TP4的步骤，将5r(0.25mmol) 和3a(0.325mmol)混合，在-20℃搅拌反应十五分钟。利用柱层析法分离得到无色油状产物25(98mg,71％).1H-NMR(400MHz,CDCl3):δ＝7.05–6.98 (m,2H),6.88–6.82(m,2H),6.46(s,1H),5.85(ddt,J＝16.9,10.2,6.6Hz,1H), 5.11–4.95(m,2H),4.22(q,J＝7.1Hz,2H),3.97(t,J＝6.5Hz,2H),2.30–2.19 (m,2H),1.97–1.82(m,2H),1.51–1.36(m,6H),1.26(m,9H),0.98–0.92(m, 6H),0.84(t,J＝7.3Hz,9H).13C-NMR(100MHz,CDCl3):δ＝173.2,168.1,158.6,138.1,137.9,129.8,127.9,115.3,114.3,67.4,60.5,30.3,29.2,28.6,27.5,14.5,13.8,12.2.HR-MS(EI)m/z calcd for C28H46O3Sn[M+H+]551.2542,found 551.2547.
Ethyl(Z)-3-(tributylstannyl)hept-2-enoate(26)
The general procedure TP4 was followed using 5s(0.25mmol)and 3a(0.325mmol)at-20℃for 15min.Purification by column chromatography(PE)yielded 26(85mg,76％)as a colorless oil.(根据一般程序TP4的步骤，将5s(0.25mmol) 和3a(0.325mmol)混合，在-20℃搅拌反应十五分钟。利用柱层析法分离得到无色油状产物26(85mg,76％).1H-NMR(400MHz,CDCl3):δ＝6.36(t,J＝1.2 Hz,1H),4.17(q,J＝7.1Hz,2H),2.39(t,J＝6.7Hz,2H),1.51–1.40(m,6H), 1.38–1.24(m,13H),0.97–0.93(m,6H),0.89(dd,J＝13.6,6.4Hz,12H). 13C-NMR(100MHz,CDCl3):δ＝176.1,168.1,128.4,60.3,40.2,31.5,29.4,27.6, 22.5,14.5,14.1,13.9,11.2.HR-MS(EI)m/z calcd for C21H42O2Sn[M+H+] 447.2280,found 447.2284.
Ethyl(Z)-2-benzyl-3-(tributylstannyl)but-2-enoate(27)
The general procedure TP5 was followed using 5an(0.25mmol)and 3a(0.325 mmol)at 0℃for 1h.Purification by column chromatography(petroleumether/EtOAc 100:1)yielded 27(85mg,69％)as a colorless oil.(根据一般程序 TP5的步骤，将5an(0.25mmol)和3a(0.325mmol)混合，在0℃搅拌反应一小时。利用柱层析法分离得到无色油状产物27(85mg,69％).1H-NMR(400 MHz,CDCl3):δ＝7.24(dd,J＝8.9,5.8Hz,2H),7.14(dd,J＝13.6,7.1Hz,3H), 4.11(q,J＝7.1Hz,2H),3.84(s,2H),2.19–2.03(m,3H),1.55–1.41(m,6H), 1.30(dt,J＝14.7,7.3Hz,6H),1.16(t,J＝7.1Hz,3H),1.02–0.90(m,6H),0.88 (t,J＝7.3Hz,9H).13C-NMR(100MHz,CDCl3):δ＝169.1,165.1,140.5,137.9,128.3,128.2,125.8,60.9,33.6,29.5,27.7,22.9,14.3,14.0,12.0.HR-MS(EI)m/z calcdfor C25H42O2Sn[M+H+]494.2207,found 494.2209.
Ethyl(Z)-3-(tributylstannyl)-2-[4-(trifluoromethyl)benzyl]but-2-enoate(28)
The general procedure TP5 was followed using 5at(0.15mmol)and 3a(0.195 mmol)at 0℃for 1h.Purification by column chromatography(PE)yielded 28(62 mg,73％)as a colorless oil.(根据一般程序TP5的步骤，将5at(0.15mmol) 和3a(0.195mmol)混合，在0℃搅拌反应一小时。利用柱层析法分离得到无色油状产物28(62mg,73％)。1H-NMR(400MHz,CDCl3):δ＝7.49(d,J＝8.1 Hz,2H),7.23(d,J＝8.0Hz,2H),4.11(q,J＝7.1Hz,2H),3.88(s,2H),2.17– 2.06(m,3H),1.52–1.42(m,6H),1.33–1.27(m,6H),1.16(t,J＝7.1Hz,3H), 0.99–0.90(m,6H),0.88(t,J＝7.3Hz,9H).13C-NMR(100MHz,CDCl3):δ＝168.7,166.4,144.8,137.0128.5,128.2(q,2JC-F＝32.4Hz),125.3(q,3JC-F＝3.8 Hz),124.5(q,1JC-F＝272.0Hz),61.0,33.6,29.5,27.7,23.0,14.3,13.9,12.0. 19F-NMR(376MHz,CDCl3):δ＝-62.30(s).HR-MS(EI)m/z calcd for C26H41F3O2Sn[M+H+]562.2081,found562.2082.
Ethyl(Z)-2-(3,4-dichlorobenzyl)-3-(tributylstannyl)but-2-enoate(29)
The general procedure TP5 was followed using 5au(0.25mmol)and 3a(0.325 mmol)at 0℃for 1h.Purificationby column chromatography(PE)yielded29(118 mg,84％)as a colorless oil.(根据一般程序TP5的步骤，将5au(0.25mmol) 和3a(0.325mmol)混合，在0℃搅拌反应一小时。利用柱层析法分离得到无色油状产物29(118mg,84％)。1H-NMR(400MHz,CDCl3):δ＝7.29(d,J＝8.2 Hz,1H),7.21(d,J＝1.8Hz,1H),6.95(dd,J＝8.3,1.9Hz,1H),4.12(q,J＝7.1 Hz,2H),3.77(s,2H),2.16–2.05(m,3H),1.53–1.40(m,6H),1.34–1.26(m, 6H),1.18(t,J＝7.1Hz,3H),1.01–0.91(m,6H),0.88(t,J＝7.3Hz,9H). 13C-NMR(100MHz,CDCl3):δ＝168.6,166.6,140.9,136.8,132.3,130.2,130.2,129.7,127.6,61.0,32.8,29.4,27.6,23.0,14.3,13.9,12.0.HR-MS(EI)m/z calcd forC25H40Cl2O2Sn[M+H+]562.1427,found 562.1429.
Ethyl(Z)-2-[2-(thiophen-3-yl)ethyl]-3-(tributylstannyl)but-2-enoate(30)
The general procedure TP5 was followed using 5t(0.25mmol)and 3a(0.325mmol)at 0℃for 1h.Purification by column chromatography(PE)yielded 30(67 mg,52％)as a colorless oil.(根据一般程序TP5的步骤，将原料5t(0.25mmol) 和3a(0.325mmol)混合，在0℃搅拌反应一小时。利用柱层析法分离得到产物无色油状产物30(67mg,52％)。1H-NMR(400MHz,CDCl3):δ＝7.22(dd,J＝ 4.9,2.9Hz,1H),6.94(dd,J＝4.9,1.2Hz,1H),6.92–6.88(m,1H),4.17(q,J＝ 7.1Hz,2H),2.76–2.66(m,4H),1.91(d,J＝22.5Hz,3H),1.49–1.40(m,6H), 1.28(td,J＝7.1,3.4Hz,9H),0.92–0.86(m,15H).13C-NMR(100MHz,CDCl3): δ＝169.2,164.1,142.5,138.8,128.6,125.2,120.4,60.8,30.0,29.4,29.3,27.7, 22.1,14.5,13.9,11.8.HR-MS(EI)m/z calcd for C24H42O2SSn[M+H+]515.2000, found 515.2008.
Ethyl(Z)-2-(4-chlorophenethyl)-3-(tributylstannyl)but-2-enoate(31)
The general procedure TP5 was followed using corresponding alkenylacetate (0.25mmol)and 3a(0.325mmol)at 0℃for 1h.Purification by columnchromatography(petroleum ether/EtOAc 100:1)yielded 31(77mg,57％)as acolorless oil.(根据一般程序TP5的步骤，将原料乙酸烯基酯(0.25mmol)和 3a(0.325mmol)混合，在0℃搅拌反应一小时。利用柱层析法分离得到产物无色油状产物31(77mg,57％)。1H-NMR(400MHz,CDCl3):δ＝7.22(d,J＝8.3 Hz,2H),7.09(d,J＝8.3Hz,2H),4.16(q,J＝7.1Hz,2H),2.67(m,4H),2.04– 1.81(m,3H),1.50–1.39(m,6H),1.32–1.25(m,9H),0.95–0.84(m,15H). 13C-NMR(100MHz,CDCl3):δ＝169.1,164.4,140.6,138.3,131.7,130.1,128.4, 60.8,35.1,30.1,29.4,27.7,22.2,14.5,13.9,11.8.HR-MS(EI)m/z calcdfor C26H43ClO2Sn[M+H+]542.1974,found 542.1977.
Ethyl
(Z)-5-(4-methoxyphenoxy)-2-[1-(tributylstannyl)ethylidene]pentanoate(32)
The general procedure TP5 was followed using 5v(0.25mmol)and 3a(0.325mmol)at 0℃for 50min.Purification by column chromatography(petroleum ether/EtOAc 50:1)yielded 32(74mg,52％)as a colorless oil.(根据一般程序TP5 的步骤，将5v(0.25mmol)和3a(0.325mmol)混合，在0℃搅拌反应五十分钟。利用柱层析法分离得到无色油状产物32(74mg,52％).1H-NMR(400 MHz,CDCl3):δ＝6.81(s,4H),4.17(q,J＝7.1Hz,2H),3.88(t,J＝6.3Hz,2H), 3.76(s,3H),2.62(t,J＝7.4Hz,2H),2.11–1.99(m,3H),1.90–1.82(m,2H), 1.49–1.40(m,6H),1.28(m,9H),0.88(m,15H).13C-NMR(100MHz,CDCl3):δ＝169.3,163.9,153.8,153.3,138.8,115.5,114.8,67.9,60.8,55.9,29.4,29.1,27.6,24.4,22.3,14.5,13.9,11.8.HR-MS(EI)m/z calcd for C28H48O4Sn[M+H+] 569.2647,found569.2652.
Ethyl(Z)-5-(4-fluorophenoxy)-2-[1-(tributylstannyl)ethylidene]pentanoate (33)
The general procedure TP5 was followed using 5ai(0.25mmol)and 3a(0.325 mmol)at 0℃for 1h.Purification by column chromatography(petroleumether/EtOAc 50:1)yielded 33(112mg,81％)as a colorless oil.(根据一般程序 TP5的步骤，将5ai(0.25mmol)和3a(0.325mmol)混合，在0℃搅拌反应一小时。利用柱层析法分离得到无色油状产物33(112mg,81％)。1H-NMR(400 MHz,CDCl3):δ＝6.98–6.91(m,2H),6.87–6.75(m,2H),4.17(q,J＝7.1Hz, 2H),3.88(t,J＝6.3Hz,2H),2.63(t,J＝7.4Hz,2H),2.11–1.98(m,3H),1.91– 1.82(m,2H),1.50–1.38(m,6H),1.27(dd,J＝15.0,7.7Hz,9H),0.93–0.84(m, 15H).13C-NMR(100MHz,CDCl3):δ＝169.2,164.1,157.3(d,1JC-F＝237.7Hz),155.3(d,4JC-F＝2.0Hz),138.7,115.9(d,2JC-F＝23.0Hz),115.4(d,3JC-F＝8.0Hz), 67.9,60.8,29.4,29.0,27.6,24.3,22.3,14.5,13.9,11.8.19F-NMR(376MHz, CDCl3):δ＝-124.43(s).HR-MS(EI)m/z calcd for C27H45FO3Sn[M+H+] 556.2375,found 556.2377.
Ethyl(Z)-5-(4-chlorophenoxy)-2-[1-(tributylstannyl)ethylidene]pentanoate (34)
The general procedure TP5 was followed using 5u(0.25mmol)and 3a(0.325mmol)at 0℃for 1h.Purification by column chromatography(petroleum ether/EtOAc50:1)yielded 34(89mg,62％)as a colorless oil.(根据一般程序TP5 的步骤，将5u(0.25mmol)和3a(0.325mmol)混合，在0℃搅拌反应一小时。利用柱层析法分离得到产物无色油状产物34(89mg,62％)。1H-NMR(400 MHz,CDCl3):δ＝7.24–7.15(m,2H),6.87–6.74(m,2H),4.16(q,J＝7.1Hz, 2H),3.89(t,J＝6.3Hz,2H),2.62(t,J＝7.4Hz,2H),2.13–1.97(m,3H),1.94– 1.81(m,2H),1.49–1.39(m,6H),1.32–1.21(m,9H),0.88(m,15H).13C-NMR(100MHz,CDCl3):δ＝169.2,164.2,157.7,138.6,129.4,125.5,115.8,67.6,60.8, 29.4,28.9,27.6,24.3,22.4,14.5,13.9,11.8.HR-MS(EI)m/z calcd for C27H45ClO3Sn[M+H+]573.2152,found 573.2155.
Ethyl(Z)-5-(3,4-dichlorophenoxy)-2-[1-(tributylstannyl)ethylidene]pentano ate(35)
The general procedure TP5 was followed using 5aj(0.25mmol)and 3a(0.325 mmol)at 0℃for 1h.Purification by column chromatography(petroleumether/EtOAc 50:1)yielded 35(87mg,58％)as a colorless oil.(根据一般程序TP5 的步骤，将5aj(0.25mmol)和3a(0.325mmol)混合，在0℃搅拌反应一小时。利用柱层析法分离得到产物无色油状产物35(87mg,58％)。1H-NMR(400 MHz,CDCl3):δ＝7.30(d,J＝8.9Hz,1H),6.96(d,J＝2.8Hz,1H),6.73(dd,J＝ 8.9,2.8Hz,1H),4.17(q,J＝7.1Hz,2H),3.89(t,J＝6.2Hz,2H),2.61(t,J＝7.4 Hz,2H),2.10–1.98(m,3H),1.92–1.83(m,2H),1.49–1.37(m,6H),1.28(dd,J ＝13.6,6.7Hz,9H),0.88(m,15H).13C-NMR(100MHz,CDCl3):δ＝169.1,164.3, 158.2,138.4,133.9,130.8,123.9,116.4,114.6,67.9,60.9,29.4,28.8,27.6,24.3, 22.4,14.5,13.9,11.8.HR-MS(EI)m/z calcd for C27H44Cl2O3Sn[M+H+]606.1689,found 606.1694.
Ethyl(Z)-5-(4-cyanophenoxy)-2-[1-(tributylstannyl)ethylidene]pentanoate (36)
The general procedure TP5 was followed using 5al(0.25mmol)and 3a(0.325 mmol)at 0℃for 1h.Purification by column chromatography(petroleumether/EtOAc 20:1)yielded 36(66mg,47％)as a colorless oil.(根据一般程序TP5 的步骤，将5al(0.25mmol)和3a(0.325mmol)混合，在0℃搅拌反应一小时。利用柱层析法分离得到无色油状产物36(66mg,47％)。1H-NMR(400MHz, CDCl3):δ＝7.57(d,J＝8.9Hz,2H),6.92(d,J＝8.9Hz,2H),4.17(q,J＝7.1Hz, 2H),3.98(t,J＝6.2Hz,2H),2.64(t,J＝7.4Hz,2H),2.11–1.98(m,3H),1.96– 1.87(m,2H),1.53–1.37(m,6H),1.27(dd,J＝14.8,7.6Hz,9H),0.95–0.82(m, 15H).13C-NMR(100MHz,CDCl3):δ＝169.1,164.4,162.4,138.3,134.1,119.4, 115.2,103.9,67.7,60.8,29.4,28.6,27.6,24.2,22.3,14.4,13.9,11.8.HR-MS(EI) m/z calcd for C28H45NO3Sn[M+H+]563.2421,found 563.2424.
Benzyl(Z)-4-[2-(ethoxycarbonyl)-3-(tributylstannyl)but-2-en-1-yl]piperidin e-1-carboxylate(37)
The general procedure TP5 was followed using 5y(0.25mmol)and 3a(0.325mmol)at 0℃for 1h.Purification by column chromatography(petroleum ether/EtOAc10:1)yielded 37(89mg,56％)as a colorless oil.(根据一般程序TP5 的步骤，将5y(0.25mmol)和3a(0.325mmol)混合，在0℃搅拌反应一小时。利用柱层析法分离得到无色油状产物37(89mg,56％)。1H-NMR(400 MHz,CDCl3):δ＝7.40–7.26(m,5H),5.12(s,2H),4.18(q,J＝7.1Hz,4H),2.70 (s,2H),2.42(d,J＝6.8Hz,2H),2.11–1.94(m,3H),1.59–1.34(m,11H),1.34– 1.09(m,9H),0.92–0.84(m,15H).13C-NMR(100MHz,CDCl3):δ＝169.4, 164.5,155.4,137.6,137.1,128.6,128.0,128.0,67.1,60.8,44.5,36.8,34.2,32.1, 29.4,27.6,23.0,14.5,13.9,11.9.HR-MS(EI)m/z calcd for C32H53NO4Sn[M+H+] 636.3069,found636.3075.
Diethyl(Z)-2-[1-(tributylstannyl)ethylidene]octanedioate(38)
The general procedure TP5 was followed using 5w(0.25mmol)and 3a(0.325mmol)at 0℃for 1h.Purification by column chromatography(petroleum ether/EtOAc50:1)yielded 38(74mg,54％)as a colorless oil.(根据一般程序TP5 的步骤，将5w(0.25mmol)和3a(0.325mmol)混合，在0℃搅拌反应一小时。利用柱层析法分离得到无色油状产物38(74mg,54％)1H-NMR(400MHz, CDCl3):δ＝4.18(dd,J＝14.4,7.3Hz,2H),4.12(dd,J＝14.4,7.2Hz,2H),2.53– 2.34(m,2H),2.29(t,J＝7.6Hz,2H),2.11–1.91(m,3H),1.52–1.36(m,10H), 1.36–1.21(m,14H),0.91–0.84(m,15H).13C-NMR(100MHz,CDCl3):δ＝174.0,169.4,162.6,139.9,60.7,60.3,34.5,29.4,29.2,29.1,27.8,27.6,25.0,22.3,14.5,14.4,13.9,11.8.HR-MS(EI)m/z calcd for C26H50O4Sn[M+H+]547.2804, found547.2810.
Ethyl(Z)-5-cyano-2-[1-(tributylstannyl)ethylidene]pentanoate(39)
The general procedure TP5 was followed using 5x(0.25mmol)and 3a(0.325mmol)at 0℃for 1h.Purification by column chromatography(petroleum ether/EtOAc50:1)yielded 39(82mg,70％)as a colorless oil.(根据一般程序TP5 的步骤，将5x(0.25mmol)和3a(0.325mmol)混合，在0℃搅拌反应一小时。利用柱层析法分离得到无色油状产物39(82mg,70％)。1H-NMR(400 MHz,CDCl3):δ＝4.21(q,J＝7.1Hz,2H),2.62–2.57(m,2H),2.32(t,J＝7.1Hz, 2H),2.14–2.03(m,3H),1.80–1.73(m,2H),1.53–1.36(m,6H),1.33–1.21(m, 9H),0.99–0.81(m,15H).13C-NMR(100MHz,CDCl3):δ＝168.7,165.8,137.3,119.8,61.0,29.3,27.6,26.8,25.3,22.5,17.0,14.4,13.9,11.8.HR-MS(EI)m/z calcdfor C22H41NO2Sn[M+H+]472.2232,found472.2236.
Ethyl(Z)-5-(pivaloyloxy)-2-[1-(tributylstannyl)ethylidene]pentanoate(40)
The general procedure TP5 was followed using 5am(0.25mmol)and 3a(0.325 mmol)at 0℃for 1h.Purification by column chromatography(petroleumether/EtOAc 50:1)yielded 40(84mg,62％)as a colorless oil.(根据一般程序TP5 的步骤，将5am(0.25mmol)和3a(0.325mmol)混合，在0℃搅拌反应一小时。利用柱层析法分离得到无色油状产物40(84mg,62％)1H-NMR(400MHz, CDCl3):δ＝4.19(q,J＝7.1Hz,2H),4.06(t,J＝6.3Hz,2H),2.58–2.45(m,2H), 2.12–1.99(m,3H),1.78–1.66(m,2H),1.51–1.39(m,6H),1.32–1.25(m,9H), 1.24–1.19(m,9H),0.93–0.83(m,15H).13C-NMR(100MHz,CDCl3):δ＝ 178.7,169.1,164.1,138.7,64.2,60.8,38.9,29.4,28.7,27.6,27.4,24.5,22.2,14.5,13.9,11.8.HR-MS(EI)m/z calcd for C26H50O4Sn[M+H+]546.2731,found 546.2733.
Ethyl(Z)-6-acetoxy-2-(1-(tributylstannyl)ethylidene)hexanoate(41)
The general procedure TP5 was followed using corresponding alkenylacetate (0.25mmol)and 3a(0.325mmol)at 0℃for 1h.Purification by columnchromatography(petroleum ether/EtOAc 50:1)yielded 41(82mg,63％)as a colorlessoil.(根据一般程序TP5的步骤，将原料乙酸烯基酯(0.25mmol)和 3a(0.325mmol)混合，在0℃搅拌反应一小时。利用柱层析法分离得到产物无色油状产物41(82mg,63％)。1H-NMR(400MHz,CDCl3):δ＝4.19(q,J＝ 7.1Hz,2H),4.07(t,J＝6.7Hz,2H),2.51–2.41(m,2H),2.11–1.99(m,6H), 1.68–1.60(m,2H),1.50–1.39(m,8H),1.28(dd,J＝14.3,7.1Hz,9H),0.88(m, 15H).13C-NMR(100MHz,CDCl3):δ＝171.3,169.3,163.2,139.4,64.6,60.8, 29.4,28.6,27.6,27.4,25.8,22.3,21.1,14.5,13.9,11.8.HR-MS(EI)m/z calcd for C24H46O4Sn[M+H+]518.2418,found 518.2420.
Ethyl(Z)-2-(4-chlorophenyl)-3-(tributylstannyl)oct-2-enoate(42)
The general procedure TP5 was followed using 5z(0.25mmol)and 3a(0.325mmol)at 23℃for 6h.Purification by column chromatography(PE)yielded 42 (77mg,54％)as a colorless oil.(根据一般程序TP5的步骤，将5z(0.25mmol) 和3a(0.325mmol)混合，在23℃搅拌反应六小时。利用柱层析法分离得到无色油状产物42(77mg,54％)。1H-NMR(400MHz,CDCl3):δ＝7.36–7.26(m, 2H),7.05–6.92(m,2H),4.11(q,J＝7.1Hz,2H),2.26–2.05(m,2H),1.55– 1.43(m,6H),1.32(dd,J＝14.7,7.3Hz,6H),1.21–1.07(m,9H),0.99(m,6H), 0.90(t,J＝7.3Hz,9H),0.79(t,J＝7.0Hz,3H).13C-NMR(100MHz,CDCl3):δ＝172.6,168.4,139.6,137.1,132.6,131.1,128.1,61.1,36.3,31.9,29.5,29.3,27.7,22.5,14.4,14.0,13.9,12.1.HR-MS(EI)m/z calcd for C28H47ClO2Sn[M+H+] 571.2359,found 571.2365.
Ethyl(S,Z)-3-{4-{[2-(4-isobutylphenyl)propanoyl]oxy}phenyl}-3-(tributylsta nnyl)acrylate(43)
The general procedure TP4 was followed using 5aa(0.25mmol)and 3a(0.325 mmol)at-20℃for 15min.Purification by column chromatography(petroleumether/EtOAc 50:1)yielded 43(91mg,54％)as a colorless oil.(根据一般程序TP4 的步骤，将5aa(0.25mmol)和3a(0.325mmol)混合，在-20℃搅拌反应十五分钟。利用柱层析法分离得到无色油状产物43(91mg,54％)。1H-NMR(400 MHz,CDCl3):δ＝7.30(d,J＝8.1Hz,2H),7.14(d,J＝8.1Hz,2H),7.07–6.98 (m,2H),6.98–6.91(m,2H),6.60–6.27(m,1H),4.22(q,J＝7.1Hz,2H),3.93(q, J＝7.2Hz,1H),2.47(d,J＝7.2Hz,2H),1.87(dt,J＝13.5,6.8Hz,1H),1.60(d,J ＝7.2Hz,3H),1.43–1.33(m,6H),1.31–1.20(m,9H),0.96–0.87(m,12H), 0.83(t,J＝7.3Hz,9H).13C-NMR(100MHz,CDCl3):δ＝173.3,172.7,167.8, 150.0,143.4,141.0,137.4,131.1,129.7,127.4,127.3,121.2,60.7,45.4,45.2,30.3, 29.2,27.5,22.5,18.7,14.5,13.8,12.1.HR-MS(EI)m/z calcd for C36H54O4Sn [M+H+]671.3117,found 671.3121.
(Z)-4-[3-Ethoxy-3-oxo-1-(tributylstannyl)prop-1-en-1-yl]phenyl 4-(N,N-dipr opylsulfamoyl)benzoate(44)
The general procedure TP4 was followed using 5ab(0.25mmol)and 3a(0.325 mmol)at-20℃for 15min.Purification by column chromatography(petroleumether/EtOAc 50:1)yielded 44(133mg,71％)as a colorless oil.(根据一般程序 TP4的步骤，将5ab(0.25mmol)和3a(0.325mmol)混合，在-20℃搅拌反应十五分钟。利用柱层析法分离得到无色油状产物44(133mg,71％)。1H-NMR(400MHz,CDCl3):δ＝8.33(d,J＝8.4Hz,2H),7.95(d,J＝8.4Hz,2H), 7.19(d,J＝8.6Hz,2H),7.15–7.09(m,2H),6.76–6.25(m,1H),4.25(q,J＝7.1 Hz,2H),3.17–3.11(m,4H),1.57(dd,J＝15.1,7.5Hz,4H),1.43(ddd,J＝12.5, 8.5,6.1Hz,6H),1.34–1.22(m,9H),1.04–0.94(m,6H),0.87(dt,J＝14.5,7.3 Hz,15H).13C-NMR(100MHz,CDCl3):δ＝172.5,167.8,163.9,149.7,145.0, 144.0,133.0,131.3,130.9,127.5,127.3,121.2,60.7,50.0,29.2,27.4,22.1,14.4, 13.8,12.1,11.3.HR-MS(EI)m/z calcd for C36H55NO6SSn[M+H+]750.2845, found 750.2851.
本发明研究了有机锡试剂在碳氧键活化反应中的底物适用性和官能团兼容性等方面的考察，在该反应体系中表现出广泛的底物适用性和优秀的官能团兼容性，并且可以顺利的进行反应放大至克级规模，反应效率保持不变。烯基锡试剂具有高立体选择性以及高反应活性，该试剂可以进一步应用于具有药理学活性的天然产物以及药物分子的结构修饰，从而也进一步说明了该类烯基锡试剂，以及该合成方法学在有机化学，生物化学，药物化学领域具有潜在的应用价值。具体反应成果如图4，5所示。
显然，上述实施例仅仅是为清楚地说明所作的举例，并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (10)

1.一种多取代烯基锡试剂，其特征在于，所述多取代烯基锡试剂的结构通式：
Figure FDA0003610972640000011
其中，R1、R2独立的选自酯基、氰基、芳基、芳基杂环、烷基、H、内酰胺、烯基、杂环、药物分子或天然产物，R3选自酯基、酰胺或H。
2.根据权利要求1所述的多取代烯基锡试剂，其特征在于，所述多取代烯基锡试剂选自以下化合物之一：
Figure FDA0003610972640000012
Figure FDA0003610972640000013
Figure FDA0003610972640000021
其中，R4为H、OMe或NMe2；
R5为F、Cl或OMe；
R6为Me或TBS。
3.权利要求1-2中任一项所述的多取代烯基锡试剂的制备方法，其特征在于，包括以下步骤：在有机溶剂中，将
Figure FDA0003610972640000022
与有机锡锌试剂在催化剂作用下混合反应得到所述多取代烯基锡试剂，其中，R1、R2独立的选自酯基、氰基、芳基、芳基杂环、烷基、H、内酰胺、烯基、杂环、药物分子或天然产物，R3选自酯基、酰胺或H。
4.根据权利要求3所述的制备方法，其特征在于，所述
Figure FDA0003610972640000031
与有机锡锌试剂的摩尔比为1:1-1:3。
5.根据权利要求3所述的制备方法，其特征在于，所述有机锡锌试剂的结构式：(nBu)3Sn-MX·LiCl,其中MX为金属或金属盐；其中，金属为Li、Zn、Al；金属盐为LiCl、MgBr、ZnCl或ZnOPiv。
6.根据权利要求3所述的制备方法，其特征在于，所述有机锡锌试剂通过以下方法制备得到：
(1)，在惰性氛围中，将萘和锂碎屑混合加入有机溶剂中，混合反应；
(2)，向步骤(1)中反应液加入烷基取代的氯化锡，混合反应；
(3)，向步骤(2)中反应液加入金属盐溶液或金属，搅拌混合反应，即得所述催化剂有机锡锌试剂。
7.根据权利要求9所述的制备方法，其特征在于，所述萘、锂碎屑和三丁基氯化锡的摩尔比为0.05-0.2：6：2。
8.根据权利要求9所述的制备方法，其特征在于，步骤(2)中，所述烷基取代的氯化锡中烷基是指三甲基、乙基或三丁基。
9.根据权利要求9所述的制备方法，其特征在于，步骤(3)中，所述金属盐溶液中金属盐选自ZnCl2、ZnBr2、ZnI2、LiCl、MgBr、和ZnOPiv中的一种或多种，所述金属选自Li、Al和Zn中的一种或多种。
10.权利要求1-2中任一项所述多取代烯基锡试剂在Stille偶联反应中应用。
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