CN110668942B - 一种醇取代的(e,e)-构型的枝型共轭二烯衍生物及其制备方法 - Google Patents
一种醇取代的(e,e)-构型的枝型共轭二烯衍生物及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种醇取代的(E,E)‑构型的枝型共轭二烯衍生物及其合成方法，属于有机合成领域，该合成方法中将烯基醇化合物、缺电子烯烃、过渡金属盐催化剂、配体、氧化剂以及碱与醇作为添加剂置于有机溶剂中，于惰气氛围下加热反应，实现羟基导向下的烯基醇与缺电子烯烃的氧化偶联反应；反应经历了羟基导向下的烯基同碳位碳氢键的活化，形成双键在环外的exo‑环金属过渡态，表现出较宽的底物范围和较好的官能团兼容性。本发明的合成方法利用廉价的氨基酸作为配体，操作简单，条件温和，底物适用性广，产率可达15～82％，适用于结构较为复杂的具有特殊生物活性化合物的化学修饰，具有广泛的应用前景，在制备方法上是一种有效补充。
Description
技术领域
本发明涉及有机合成领域，具体涉及一种醇取代的(E,E)-枝型的共轭二烯衍生物及其合成方法。
背景技术
近年来，过渡金属催化下、导向基作用下的C-H键选择性官能化引起了人们极大的兴趣，在这些方法中，过渡金属可与导向基团作用并插入特定的C-H键，通过形成环金属过渡态实现特定C-H键的选择性切断和官能化；导向基策略在芳基和烷基碳氢键官能化中研究得较多，但是该策略在烯烃碳氢键的选择性转化中研究的不够充分，可能是由于烯烃的高活性和不稳定性，目前，导向基作用下烯烃碳氢键的选择性官能化仅仅局限于烯基邻位/顺式碳氢键的切断和官能化，而对于其它位置碳氢键的反应则鲜有报道。
Engle课题组报导了8-胺基喹啉酰胺导向下的烯烃同碳位的碳氢键烯基化反应，该反应通过了N,N-双配位的六员环金属过渡态(C(alkenyl)–H Activation via Six-Membered Palladacycles:Catalytic 1,3-Diene Synthesis.J.Am.Chem.Soc.2018,140,5805)。最近，Carreira课题组报导了2-吡啶甲酸的酰胺导向下的烯烃同碳位的碳氢键碘化反应，该反应主要经过了N,N-双配位的六员金属过渡态(Palladium-CatalyzedRegioselective C–H Iodination of Unactivated Alkenes.J.Am.Chem.Soc.2019,141,8758)。但是，这些方法存在一些局限性，如：1)只能通过六员环金属过渡态来实现特定碳氢键的活化；2)N,N-双配位的导向基团的安装和脱除使得反应变得繁琐，限制其应用。
烯基醇是一类常见的有机化合物，尤其在天然产物和药物中存在广泛，利用烯基醇作为原料，实现其选择性的化学转化具有重要意义，关于烯基醇类化合物的碳氢键官能化报导有限，特别是将弱配位的羟基作为导向基团，实现烯基碳氢键选择性活化和官能化，则显得更为高效和实用。
Loh课题组曾报导了烯基醇与缺电子烯烃的氧化偶联，可以得到线型的共轭二烯衍生物(Chelation versus Non-Chelation Control in the Stereoselective Alkenylsp2C-H Bond Functionalization Reaction.Angew.Chem.,Int.Ed.2017,56,5091)，反应经历了羟基导向下的烯基邻位碳氢键的活化，形成双键在环内的endo-环金属过渡态，这类方法仅适用于末端烯烃的反应，对内部烯烃则无能为力。
发明内容
本发明提供了一种醇取代的(E,E)-构型的枝型共轭二烯衍生物及其合成方法，该合成方法为羟基导向下的烯基醇与缺电子烯烃的氧化偶联反应，用于制备枝型共轭二烯；反应经历了羟基导向下的烯基同碳位碳氢键的活化，形成双键在环外的exo-环金属过渡态，表现出较宽的底物范围和较好的官能团兼容性。
一种醇取代的(E,E)-构型的枝型共轭二烯衍生物，结构式如式I、式II和式III所示：
式I中，R1为C1～8烃基、酯基取代C1～8烃基、C1～8羟烃基或C6～10芳基；R2为H、甲基或与R1连接成五元环、六元环；R3为H、环烷基、含氧杂环、C1～6烷基、烯基、联苯基或取代芳基；所述的取代芳基的取代基为C1～6的烷基、C1～6的烷氧基、或卤素；R4为酯基、酮羰基、芳基、酰胺基、膦酸酯基；式II中R5为C1～6烷基；R6为H或C1～3烷基；R7为C1～6酯基；式III中R8为C1～8烷基；R9为C1～6酯基。
本发明还提供了一种醇取代的(E,E)-构型的枝型共轭二烯衍生物的合成方法，所述醇取代的(E,E)-构型的枝型共轭二烯衍生物的合成方法为：
将烯基醇化合物、缺电子烯烃、过渡金属盐催化剂、配体、氧化剂以及碱与添加剂置于有机溶剂中，于惰气氛围下加热反应，反应结束后，反应液经后处理得到与反应物相应的式I、式II或式III所示的化合物。
反应机理如下：烯基醇中的羟基与金属钯配位后，金属钯插入到同碳位的烯基碳氢键中(氧化加成过程)，形成四元、五元或六元双键在环外的环金属过渡态，随后发生缺电子烯烃的配位和插入，再伴随β-氢消除，即得到烯基化产物。氨基酸起到了配体的作用，并促进烯基碳氢键的断裂。
优选的，所述烯基醇化合物为如式V所示的取代2-烯丙醇、如式IV所示的取代3-烯丁醇或如式VI所示的取代4-烯戊醇；
式IV中R1，R2，R3的定义与式I一致；式V中R5，R6的定义与式II一致；式VI中R8与式III一致；
所述缺电子烯烃为如式VII、式VIII或式IX所示的丙烯酸酯、取代苯乙烯、取代丙烯酰胺或烯基膦酸酯：
式VII中R4的定义与式I一致；式VIII中R7的定义与式II一致；式IX中R9与式III一致。
优选的，所述过渡金属盐催化剂为钯盐；进一步优选为，所述钯盐为醋酸钯或氯化钯。
优选的，所述配体为氨基酸；进一步优选为，所述的氨基酸N-乙酰基苯丙氨酸或N-乙酰基甘氨酸。
优选的，所述的氧化剂银盐；所述的银盐为碳酸银或氧化银；进一步优选为碳酸银。
优选的，所述的碱为碳酸铯、碳酸钾或氢氧化锂；所述添加剂为三氟乙醇或三氟异丙醇。
优选的，所述合成方法中，烯基醇化合物：缺电子烯烃：过渡金属盐催化剂：氨基酸配体：氧化剂：碱：添加剂的物质的量之比为1：1～2：0.05～0.15：0.2～0.8：1.0～2.0：0.2～0.5：5～15。
优选的，所述有机溶剂的体积用量以烯基醇化合物的物质的量计为3～5L/mol。
优选的，所述有机溶剂为甲苯、四氢呋喃、1,4-二氧六环、1,2-二氯乙烷、乙醇、二甲氧基乙烷中的一种或几种。
优选的，所述加热反应温度为50～100℃，反应时间16～24小时。
本发明所述后处理为：将反应液装柱，剩余反应液用二氯甲烷溶解转移，用硅胶进行柱层析分离，洗脱剂为体积比1：2-5的乙酸乙酯与石油醚混合液，收集含目标化合物的洗脱液，浓缩干燥得到相应目标产物。
进一步优选，本发明在相对温和的条件下，采用简单过渡金属盐作为催化剂，氨基酸作为配体，银盐作为氧化剂，碱和醇作为添加剂，从简单原料烯基醇和缺电子烯烃来制备枝型共轭二烯，反应式如下：
本发明有益效果主要体现在：
(1)本发明提供了一种利用烯基醇和缺电子烯烃高效合成枝型共轭二烯化合物的方法，得到的产物都是全新且未见报道的。
(2)本发明的合成方法，操作简单，反应条件温和，底物适用范围广泛，产率可达15～82％，应用范围广泛，具有非常好的经济价值。
(3)本发明的合成方法实现了内部烯烃的碳氢键的选择性切断和官能化，大大拓宽了烯烃选择性性转化的范围，同时利用廉价的氨基酸作为配体，原料来源广泛，经济效益更高，生产压力更小。
(4)本发明的合成原料经济易得，适用于结构较为复杂的具有特殊生物活性化合物的化学修饰，具有广泛的应用前景，在制备方法上是一种有效补充。
附图说明
图1为本发明实施例1所得产物的核磁氢谱；
图2为本发明实施例27所得产物的核磁氢谱；
图3为本发明实施例29所得产物的核磁氢谱。
具体实施方式
下面结合实施例对本发明作进一步说明，下述实施例中所使用的实验方法如无特殊说明，均为常规方法，实施例中所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol，10.0当量)、1,4-二噁烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(46.8mg,收率69％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.26(d,J＝16.5Hz,1H),6.01(t,J＝7.5Hz,1H),5.85(d,J＝16.0Hz,1H),4.15(t,J＝7.0Hz,2H),3.65(t,J＝7.0Hz,2H),2.55(t,J＝7.0Hz,2H),2.23-2.29(m,2H),1.62-1.68(m,2H),1.37-1.44(m,2H),1.03-1.06(m,3H),0.93-0.96(m,3H).13C NMR(125MHz,CDCl3):δ＝167.61,148.45,146.27,132.64,115.66,64.23,61.16,30.77,29.97,22.24,19.18,13.72,13.69.HR-MS(ESI):m/zcalculated for C13H22O3[M+H]+:227.1642,found:227.1642.FTIR(KBr,cm-1):3786.32,1731.91,1703.94,1519.16,1514.97,1486.51,1416.54,1385.07,1172.81,982.04。
实施例2：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(30.4mg，收率39％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.19-7.31(m,6H),5.95(t,J＝7.5Hz,1H),5.84(d,J＝16.0Hz,1H),5.12(s,2H),3.58(t,J＝7.0Hz,2H),2.48(t,J＝7.0Hz,2H),2.15-2.21(m,2H),0.96(t,J＝7.5Hz,3H).13C NMR(125MHz,CDCl3):δ＝166.23,148.03,145.74,135.12,131.61,127.55,127.24,127.18,114.28,65.17,60.14,28.91,21.27,12.66.HR-MS(ESI):m/z calculated for C16H20O3[M+H]+:261.1485,found:261.1474.FTIR(KBr,cm-1):3507.51,3417.34,1770.32,1714.67,1621.60,1385.53,1258.80,1020.55,802.74。
实施例3：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(33.3mg，收率44％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.36(d,J＝16.0Hz,1H),6.08(t,J＝7.5Hz,1H),5.90(d,J＝16.0Hz,1H),4.53(q,J＝8.5Hz,2H),3.67(t,J＝7.0Hz,2H),2.57(t,J＝7.0Hz,2H),2.25-2.31(m,2H),1.05(t,J＝7.5Hz,3H).13C NMR(125MHz,CDCl3):δ＝164.62,150.06,147.28,131.66,122.12(q,JC-F＝275.6Hz),112.35,60.10,59.24(q,JC-F＝36.3Hz),28.83,21.39,12.56.HR-MS(ESI):m/z calculated for C11H15F3O3[M+H]+:253.1046,found:253.1041.FTIR(KBr,cm-1):3654.05,3500.11,3417.70,1841.92,1698.41,1360.26,1257.70,987.79。
实施例4：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(53.4mg，收率78％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.23(d,J＝16.0Hz,1H),5.96(t,J＝7.5Hz,1H),5.84(d,J＝16.0Hz,1H),4.23(t,J＝4.0Hz,2H),3.56-3.59(m,4H),3.34(s,3H),2.48(t,J＝7.0Hz,2H),2.16-2.22(m,2H),0.97(t,J＝7.5Hz,3H).13C NMR(125MHz,CDCl3):δ＝166.43,148.05,145.68,131.65,114.18,69.58,62.34,60.10,57.99,28.95,21.26,12.66.HR-MS(ESI):m/z calculated for C12H20O4[M+H]+:229.1434,found:229.1430.FTIR(KBr,cm-1):3507.52,3479.32,3459.67,2395.83,1661.57,1372.53,1337.55,985.06。
实施例5：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(55.7mg，收率73％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.26(d,J＝15.5Hz,1H),5.99(t,J＝7.5Hz,1H),5.87(d,J＝16.0Hz,1H),4.20(dd,J＝3.5Hz,J＝11.5Hz,1H),4.12-4.14(m,1H),4.04(dd,J＝7.0Hz,J＝11.5Hz,1H),3.87(dd,J＝7.0Hz,J＝15.0Hz,1H),3.76-3.80(m,1H),3.60(t,J＝7.0Hz,2H),2.52(t,J＝7.0Hz,2H),2.22(t,J＝7.5Hz,2H),1.85-2.01(m,4H),0.99-1.03(m,3H).13C NMR(125MHz,CDCl3):δ＝166.42,148.03,145.62,131.68,114.19,75.65,67.43,65.39,60.07,28.97,26.99,24.64,21.25,12.67.HR-MS(ESI):m/z calculated for C14H22O4[M+H]+:255.1591,found:255.1581.FTIR(KBr,cm-1):3654.35,1714.54,1682.50,1505.51,1482.85,1372.85,1295.26,1169.90。
实施例6：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(36.3mg，收率54％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.11-7.14(m,1H),6.15(d,J＝16.0Hz,1H),6.03(t,J＝7.0Hz,1H),3.63(t,J＝7.0Hz,2H),2.52-2.58(m,4H),2.24-2.27(m,2H),1.61(t,J＝7.0Hz,2H),1.29-1.30(m,4H),1.02-1.05(m,3H),0.86-0.89(m,3H).13C NMR(125MHz,CDCl3):δ＝200.30,146.19,145.53,132.01,123.15,60.19,39.63,30.51,28.96,23.16,21.47,21.40,12.93,12.68.HR-MS(ESI):m/z calculated forC14H24O2[M+H]+:225.1849,found:225.1847.FTIR(KBr,cm-1):3654.28,3354.70,2020.28,1557.40,1505.35,1393.07,1360.46,987.93。
实施例7：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(59.0mg，收率75％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝6.97-7.07(m,1H),5.91(t,J＝7.0Hz,1H),5.56(td,J＝3.5Hz,J＝18.0Hz,1H),4.03-4.07(m,4H),3.57-3.63(m,2H),2.51-2-55(m,2H),2.19-2.24(m,2H),1.28-1.32(m,6H),0.98-1.93(m,3H).13C NMR(125MHz,CDCl3):δ＝151.54(d,JC-P＝5.0Hz),144.56,132.12(d,JC-P＝22.5Hz),109.57(d,JC-P＝191.3Hz),60.73,60.69,59.99,28.75,21.15,15.39,15.34,12.68.HR-MS(ESI):m/z calculated for C12H23O4P[M+H]+:263.1407,found:263.1403.FTIR(KBr,cm-1):3654.34,3444.53,3418.18,2225.34,1770.27,1455.31,1332.28,1232.70,1026.55。
实施例8：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(38.2mg，收率54％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.18-7.24(m,4H),6.62(d,J＝16.0Hz,1H),6.38(d,J＝16.5Hz,1H),5.69(t,J＝7.5Hz,1H),3.65(t,J＝7.0Hz,2H),2.58(t,J＝7.0Hz,2H),2.14-2.20(m,2H),0.96(t,J＝7.5Hz,3H).13C NMR(125MHz,CDCl3):δ＝138.03,135.20,132.28,132.18,131.53,127.70,126.69,123.47,60.60,29.00,20.89,13.17.HR-MS(ESI):m/z calculated for C14H17ClO[M-H2O]+H]+:219.0914,found:219.0928.FTIR(KBr,cm-1):3417.81,3331.79,1732.22,1661.67,1621.68,1557.31,1505.40,1258.25,1088.67,1012.38,805.60,422.27。
实施例9：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(41.6mg，收率65％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.29(d,J＝15.5Hz,1H),6.43(d,J＝15.5Hz,1H),6.00(t,J＝7.5Hz,1H),3.69(s,3H),3.66(t,J＝7.0Hz,2H),3.25(s,3H),2.59(t,J＝7.0Hz,2H),2.21-2.27(m,2H),1.01(t,J＝7.5Hz,3H).13C NMR(125MHz,CDCl3):δ＝166.54,146.36,144.58,131.92,112.12,60.71,60.34,31.50,29.21,21.19,12.75.HR-MS(ESI):m/z calculated for C11H19NO3[M+H]+:214.1438,found:214.1440.FTIR(KBr,cm-1):3654.39,3472.87,1704.16,1698.63,1694.38,1557.41,1442.85,1403.31,1392.46,1179.40,1002.51。
实施例10：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(42.0mg，收率71％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.20(d,J＝15.0Hz,1H),6.28(d,J＝15.0Hz,1H),5.93(t,J＝7.5Hz,1H),3.63(t,J＝7.0Hz,2H),3.07(s,3H),2.99(s,3H),2.57(t,J＝7.0Hz,2H),2.18-2.24(m,2H),1.00(t,J＝7.5Hz,3H).13C NMR(125MHz,CDCl3):δ＝166.43,145.25,143.46,131.86,113.76,60.37,36.42,34.85,29.27,21.09,12.79.HR-MS(ESI):m/z calculated for C11H19NO2[M+H]+:198.1489,found:198.1492.FTIR(KBr,cm-1):3654.23,3550.31,3500.31,3417.93,1842.04,1557.30,1428.03,1385.30,1360.47,979.54。
实施例11：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(36.6mg，收率48％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.24(d,J＝17.0Hz,1H),6.03(t,J＝7.5Hz,1H),5.99(d,J＝16.0Hz,1H),4.15(t,J＝6.7Hz,2H),3.64-3.69(m,2H),2.99-3.05(m,1H),2.22(q,J＝7.0Hz,2H),1.64-1.67(m,2H),1.37-1.43(m,4H),1.33-1.37(m,2H),1.13(d,J＝7.2Hz,3H),0.95(t,J＝7.5Hz,3H),0.91(t,J＝7.0Hz,3H).13C NMR(125MHz,CDCl3):δ＝166.33,145.15,139.50,136.45,116.10,64.81,63.22,35.16,30.60,29.77,27.30,21.42,18.17,14.40,12.90,12.73.HR-MS(ESI):m/z calculated forC16H28O3[M+H]+:269.2111,found:269.2112.FTIR(KBr,cm-1):3132.60,2919.35,1694.17,1667.46,1633.77,1505.04,1455.17,1400.20。
实施例12：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(37.5mg，收率52％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.28(d,J＝16.0Hz,1H),6.13-6.17(m,1H),5.82(d,J＝16.0Hz,1H),4.14(td,J＝1.5Hz,J＝7.0Hz,2H),3.63-3.68(m,1H),2.38-2.49(m,2H),1.85(d,J＝7.0Hz,3H),1.61-1.67(m,2H),1.48-1.55(m,2H),1.38-1.42(m,2H),0.97-1.00(m,3H),0.92-0.96(m,3H).13C NMR(125MHz,CDCl3):δ＝167.59,148.62,139.22,134.94,115.70,71.91,64.24,34.12,30.78,30.10,19.19,15.08,13.74,10.15.HR-MS(ESI):m/z calculated for C14H24O3[M+H]+:241.1798,found:241.1795.FTIR(KBr,cm-1):3473.28,1790.01,1747.00,1651.65,1557.38,1633.28,1403.25,1385.30,1337.13,984.16。
实施例13：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(50.3mg，收率52％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.27(d,J＝15.5Hz,1H),6.05(t,J＝7.5Hz,1H),5.78(d,J＝16.0Hz,1H),4.10-4.17(m,2H),3.46(q,J＝5.5Hz,1H),2.41(d,J＝7.0Hz,2H),2.23(m,2H),1.89(d,J＝8.0Hz,1H),1.61-1.79(m,6H),1.39(q,J＝7.5Hz,4H),1.07-1.30(m,10H),0.94(t,J＝7.5Hz,3H),0.88(t,J＝7.0Hz,3H).13C NMR(125MHz,CDCl3):δ＝166.53,147.77,144.45,133.10,114.78,73.40,63.20,42.80,30.55,29.80,28.14,27.89,27.08,25.52,25.31,25.15,21.51,18.18,12.98,12.74.HR-MS(ESI):m/z calculated for C22H38O3[M+H]+:373.2713,found:373.2703.FTIR(KBr,cm-1):3626.38,3616.64,3425.22,2972.61,2925.99,1462.67,1454.96,1384.57,1087.64,800.54。
实施例14：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(40.9mg，收率46％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.28(d,J＝16.0Hz,1H),6.04(t,J＝7.5Hz,1H),5.81(d,J＝16.0Hz,1H),4.13-4.16(m,2H),3.77-3.81(m,1H),2.35-2.46(m,2H),2.23(q,J＝7.5Hz,2H),1.77-1.83(m,1H),1.61-1.67(m,2H),1.39-1.44(m,4H),1.24-1.31(m,6H),0.94(t,J＝7.5Hz,6H),0.88(t,J＝6.5Hz,6H).13C NMR(125MHz,CDCl3):δ＝166.55,147.82,144.38,132.66,114.85,67.56,63.22,45.49,34.41,30.55,29.78,28.19,27.88,23.70,22.54,21.51,20.91,18.18,12.97,12.73.HR-MS(ESI):m/z calculated for C20H36O3[M+H]+:347.2557,found:347.2546.FTIR(KBr,cm-1):3564.70,3417.21,2972.05,2900.15,1404.08,1393.46,1065.67,1049.40。
实施例15：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(53.1mg，收率56％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.19-7.28(m,6H),5.92(t,J＝7.5Hz,1H),5.83(d,J＝16.0Hz,1H),4.72(t,J＝7.0Hz,1H),4.08(t,J＝6.5Hz,2H),2.70(dd,J＝7.5Hz,J＝14.0Hz,1H),2.56(dd,J＝6.0Hz,J＝13.5Hz,1H),1.97-2.01(m,2H),1.83-1.88(m,1H),1.56-1.62(m,2H),1.31-1.39(m,2H),1.13-1.21(m,6H),0.89(t,J＝7.5Hz,3H),0.79(t,J＝7.0Hz,3H).13C NMR(125MHz,CDCl3):δ＝166.58,147.63,144.96,142.89,131.83,127.37,126.68,124.77,114.37,71.86,63.22,35.94,30.51,29.79,27.91,27.61,21.45,18.19,12.97,12.74.HR-MS(ESI):m/z calculated for C22H32O3[M+H]+:367.2244,found:367.2231.FTIR(KBr,cm-1):3470.72,3383.63,2484.67,1732.62,1673.61,1557.21,1417.04,1385.26。
实施例16：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(47.6mg，收率48％)。
核磁共振谱图分峰如下：。1H NMR(500MHz,CDCl3):δ＝7.23-7.30(m,3H),7.14(d,J＝7.5Hz,2H),5.99(t,J＝7.5Hz,1H),5.90(d,J＝16.0Hz,1H),4.76(t,J＝7.0Hz,1H),4.16(t,J＝6.5Hz,2H),2.76(dd,J＝8.0Hz,J＝14.0Hz,1H),2.61(dd,J＝6.0Hz,J＝14.0Hz,1H),2.33(s,3H),2.04-2.10(m,1H),1.94-1.96(m,2H),1.63-1.69(m,2H),1.38-1.46(m,2H),1.19-1.28(m,6H),0.96(t,J＝7.5Hz,3H),0.87(t,J＝7.0Hz,3H).13C NMR(125MHz,CDCl3):δ＝166.59,147.61,144.88,139.95,136.34,131.95,128.03,124.71,114.70,71.74,63.20,35.91,30.54,29.80,27.94,27.64,21.47,20.09,18.19,12.98,12.74.HR-MS(ESI):m/z calculated for C23H34O3[M+H]+:359.2581,found:359.2583.FTIR(KBr,cm-1):3742.37,3444.58,2988.72,1621.41,1417.21,1304.80,1175.05,984.38。
实施例17：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(57.1mg，收率55％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.26-7.29(m,3H),6.86(d,J＝8.7Hz,2H),5.98(t,J＝7.4Hz,1H),5.89(d,J＝16.0Hz,1H),4.74(t,J＝6.9Hz,1H),4.15(t,J＝6.7Hz,2H),3.79(s,3H),2.76(dd,J＝13.7Hz,J＝7.6Hz,1H),2.60(dd,J＝13.7Hz,J＝6.2Hz,1H),2.05-2.07(m,2H),1.92-1.96(m,1H),1.63-1.68(m,2H),1.38-1.44(m,2H),1.20-1.30(m,6H),0.96(t,J＝7.4Hz,3H),0.87(t,J＝7.1Hz,3H).13C NMR(125MHz,CDCl3):δ＝166.61,158.15,147.70,144.84,135.09,131.95,126.00,114.68,112.72,71.48,63.21,54.25,35.91,30.53,29.79,27.94,27.64,21.46,18.19,12.97,12.74.HR-MS(ESI):m/z calculated for C23H34O4[M+H]+:375.2530,found:375.2521.FTIR(KBr,cm-1):3362.10,1698.59,1614.59,1434.71,1247.38,1178.00,1047.83,880.44,832.29,666.62。
实施例18：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(50.4mg，收率48％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.34-7.26(m,5H),6.00(t,J＝7.5Hz,1H),5.87(d,J＝15.9Hz,1H),4.78(t,J＝6.9Hz,1H),4.16(t,J＝6.7Hz,2H),2.74(dd,J＝13.8Hz,J＝7.6Hz,1H),2.60(dd,J＝13.8Hz,J＝6.2Hz,1H),2.06(d,J＝26.1Hz,2H),1.94-1.88(m,1H),1.68-1.64(m,2H),1.42(dd,J＝15.0Hz,7.5Hz,2H),1.32-1.22(m,6H),0.96(t,J＝7.4Hz,3H),0.87(t,J＝7.1Hz,3H).13C NMR(125MHz,CDCl3):δ＝166.50.147.46,145.12,141.32,132.33,131.46,127.47,126.19,114.80,71.74,63.29,35.94,30.53,29.78,27.96,27.63,21.46,18.19,12.97,12.74.HR-MS(ESI):m/zcalculated for C22H31ClO3[M+H]+:379.2034,found:379.2031.FTIR(KBr,cm-1):3417.55,2970.43,2924.78,1633.28,1311.51,1183.92,1090.59,1049.75,880.77.
实施例19：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色固体产物(70.6mg，收率60％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.55-7.58(m,4H),7.41-7.44(m,4H),7.25-7.35(m,2H),6.01(t,J＝7.4Hz,1H),5.92(d,J＝15.9Hz,1H),4.84(t,J＝6.8Hz,1H),4.15(t,J＝6.7Hz,2H),2.80(dd,J＝13.8Hz,J＝7.7Hz,1H),2.66(dd,J＝13.8Hz,J＝6.1Hz,1H),2.18(s,1H),2.05-2.12(m,1H),1.91-1.98(m,1H),1.62-1.68(m,2H),1.38-1.41(m,2H),1.21-1.29(m,6H),0.94(t,J＝7.4Hz,3H),0.84(t,J＝6.9Hz,3H).13C NMR(125MHz,CDCl3):δ＝166.59,147.64,145.04,141.91,139.77,139.62,131.78,127.73,126.27,126.07,126.02,125.24,114.73,71.61,63.24,35.93,30.52,29.77,27.95,27.64,21.44,18.18,12.95,12.73.HR-MS(ESI):m/z calculated for C28H36O3[M+H]+:421.2737,found:421.2732.FTIR(KBr,cm-1):3606.29,3418.11,1633.44,1434.93,1359.46,1049.89,880.53,773.38.
实施例20：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(44.7mg，收率47％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.26-7.30(d,J＝12.5Hz,1H),6.01(t,J＝7.5Hz,1H),5.89(d,J＝15.8Hz,1H),5.19(d,J＝9.8Hz,1H),4.49(dd,J＝15.2Hz,J＝7.0Hz,1H),4.15(t,J＝6.7Hz,2H),2.56(dd,J＝13.7,7.3Hz,1H),2.43(dd,J＝13.7,6.2Hz,1H),2.23(q,J＝7.4Hz,2H),1.70(s,3H),1.66(dd,J＝14.4,7.4Hz,2H),1.62(s,3H),1.41(dd,J＝14.9,7.5Hz,4H),1.30(d,J＝7.2Hz,4H),0.95(t,J＝7.4Hz,3H),0.89(t,J＝6.9Hz,3H).13C NMR(125MHz,CDCl3):δ＝166.64,147.91,144.36,134.51,132.13,126.32,114.67,66.51,63.16,33.78,30.59,29.77,28.23,27.84,24.74,21.52,18.18,17.36,12.99,12.73.HR-MS(ESI):m/z calculated for C20H34O3[M+H]+:323.2581,found:323.2587.FTIR(KBr,cm-1):3851.13,3286.23,2970.43,2922.78,1629.78,1049.76,880.79,781.42.
实施例21：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(35.3mg，收率42％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.26-7.31(m,1H),6.03(t,J＝7.5Hz,1H),5.90(d,J＝16Hz,0.6H),5.85(d,J＝15.5Hz,0.4H),5.62-5.69(m,0.4H),5.54-5.59(m,0.6H),5.48-5.52(m,0.4H),5.41-5.45(m,0.6H),4.60(q,J＝7.5Hz,0.7H),4.15(t,J＝6.5Hz,2H),2.53-2.60(m,1H),2.42-2.46(m,1H),2.21-2.27(m,2H),1.62-1.69(m,6H),1.39-1.45(m,4H),1.30(t,J＝3.5Hz,3H),0.95(t,J＝7.5Hz,3H),0.89(t,J＝6.5Hz,3H).13C NMR(125MHz,CDCl3):δ＝166.61,147.85,147.79,144.48,144.44,132.27,132.10,131.94,131.60,126.09,125.77,114.79,114.71,70.57,65.24,63.19,33.75,33.52,30.56,29.77,28.26,28.20,27.85,27.82,21.52,21.50,18.18,16.62,12.98,12.73,12.44.HR-MS(ESI):m/zcalculated for C19H32O3[M+H]+:309.2424,found:309.2423.FTIR(KBr,cm-1):3584.88,3264.14,2969.64,2924.43,1683.58,1504.73,1307.18,1088.28,1049.17,880.56,666.73.
实施例22：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(23.6mg，收率33％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.23(d,J＝16.0Hz,1H),6.24(t,J＝4.0Hz,1H),5.89(d,J＝16.0Hz,1H),4.14(t,J＝6.5Hz,2H),3.72(dd,J＝3.0Hz,J＝10.5Hz,1H),3.55(t,J＝9.5Hz,1H),2.63(s,1H),2.21-2.23(m,2H),2.02-2.05(m,1H),1.63-1.67(m,5H),1.37-1.44(m,2H),0.94(t,J＝7.5Hz,3H).13C NMR(125MHz,CDCl3):δ＝167.72,147.16,140.99,134.67,115.00,64.24,63.65,36.22,30.79,26.40,23.59,19.20,17.24,13.75.HR-MS(ESI):m/z calculated for C12H20O3[M+H]+:235.1305,found:235.1321.FTIR(KBr,cm-1):3550.50,3472.87,1732.26,1714.52,1651.71,1626.64,1463.20,1416.88,1393.11,1372.51,1172.46.
实施例23：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(42.8mg，收率52％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.29-7.38(m,5H),7.22-7.23(m,1H),6.89(s,1H),5.97(d,J＝15.5Hz,1H),4.12(t,J＝6.5Hz,2H),3.77(t,J＝7.0Hz,2H),2.76(t,J＝7.5Hz,2H),1.57-1.63(m,2H),1.33-1.39(m,2H),0.88(t,J＝7.5Hz,3H).13C NMR(125MHz,CDCl3):δ＝167.35,148.70,141.09,136.12,134.49,129.13,128.57,128.16,117.62,64.42,61.22,30.79,30.51,19.21,13.76.HR-MS(ESI):m/zcalculated for C17H22O3[M+H]+:275.1642,found:275.1642.FTIR(KBr,cm-1):3444.75,3418.02,3382.09,1747.06,1634.03,1403.31,1385.36,1337.39,996.77.
实施例24：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应24小时后，反应液经直接柱层析分离后得到黄色固体产物(81.3mg，收率62％)
核磁共振谱图分峰如下：。1H NMR(500MHz,CDCl3):δ＝7.18(d,J＝7.0Hz,1H),7.16(s,1H),6.99(dd,J＝2.0Hz,J＝8.5Hz,1H),6.89(d,J＝1.0Hz,1H),5.93(t,J＝7.5Hz,1H),5.81(d,J＝15.5Hz,1H),5.69(t,J＝6.5Hz,1H),3.62(t,J＝7.5Hz,2H),3.30(dd,J＝6.5Hz,J＝13.5Hz,1H),3.19(dd,J＝7.0Hz,J＝14.5Hz,1H),2.79-2.94(m,3H),2.52(t,J＝7.0Hz,2H),2.28(d,J＝12.5Hz,1H),2.18-2.22(m,2H),1.63-1.78(m,4H),1.42-1.46(m,2H),1.29-1.35(m,2H),1.22(s,3H),1.21(s,6H),1.01(t,J＝7.5Hz,3H),0.95(s,3H).13CNMR(125MHz,CDCl3):δ＝165.67,146.16,144.61,143.82,143.62,133.82,131.34,125.91,123.14,122.83,117.19,60.27,48.83,44.16,37.28,36.60,36.44,35.13,32.40,29.16,24.28,22.96,21.11,17.94,17.81,17.60,12.78.HR-MS(ESI):m/z calculated forC29H43NO2[M+H]+:438.3367,found:438.3359.FTIR(KBr,cm-1):3626.78,3585.28,3564.71,1651.64,1633.92,1470.74,1463.01,1400.05.
实施例25：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应36小时后，反应液经直接柱层析分离后得到黄色油状产物(49.6mg，收率54％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.37-7.29(d,J＝13.0Hz,1H),6.01(t,J＝7.5Hz,1H),5.87(d,J＝15.9Hz,1H),5.38(t,J＝6.6Hz,1H),5.09(t,J＝6.7Hz,1H),4.67(d,J＝7.1Hz,2H),3.66(t,J＝7.0Hz,2H),2.56(t,J＝7.0Hz,2H),2.23-2.29(m,2H),2.09-2.13(m,2H),2.04-2.07(m,2H),1.72(s,3H),1.68(s,3H),1,60(s,3H),1.04(t,J＝7.5Hz,3H).13C NMR(125MHz,CDCl3):δ＝166.47,147.50,145.34,141.24,131.62,130.81,122.76,117.37,114.64,60.26,60.15,38.54,28.95,25.29,24.67,21.25,16.68,15.49,12.69.HR-MS(ESI):m/z calculated for C19H30O3[M+H]+:307.2268,found:307.2271.FTIR(KBr,cm-1):3626.76,3585.23,3133.10,1682.42,1633.80,1505.12,1462.92,1400.22.
实施例26：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(14.4mg，收率20％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.22(d,J＝16.0Hz,1H),6.24(d,J＝16.0Hz,1H),5.89(t,J＝7.5Hz,1H),4.95(q,J＝6.5Hz,1H),4.15(t,J＝7.0Hz,2H),2.20-2.25(m,2H),1.62-1.68(m,2H),1.57-1.58(m,2H),1.44-1.48(m,2H),1.39-1.40(d,J＝7.0Hz,3H),0.92-0.96(m,6H).13C NMR(125MHz,CDCl3):δ＝166.60,143.85,139.26,138.66,116.76,64.45,63.17,29.78,29.31,21.57,20.97,18.17,12.83,12.73.HR-MS(ESI):m/z calculated for C14H24O3[M+H]+:241.1798,found:241.1794.FTIR(KBr,cm-1):3616.60,3550.07,2924.32,1682.93,1462.87,1385.04,1173.40,1089.05,1049.32,880.76,666.71.
实施例27：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(23.5mg，收率37％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.25(d,J＝15.0Hz,1H),6.07(d,J＝15.5Hz,1H),6.03-6.09(m,1H),4.37(s,2H),4.16(t,J＝6.5Hz,2H),2.28-2.34(m,2H),1.62-1.68(m,2H),1.37-1.45(m,2H),1.07(t,J＝7.5Hz,3H),0.95(t,J＝7.5Hz,3H).13C NMR(125MHz,CDCl3):δ＝166.51,145.61,145.27,134.27,115.91,63.22,55.90,29.76,20.92,18.16,12.85,12.72.HR-MS(ESI):m/zcalculated for C12H20O3[M+H]+:213.1485,found:213.1478.FTIR(KBr,cm-1):3441.21,3417.76,3332.43,2966.36,2925.54,2358.45,1694.28,1682.65,1170.32,1047.71.
实施例28：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(29.2mg，收率43％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.25(d,J＝16.0Hz,1H),6.03-6.08(m,2H),6.03(d,J＝7.5Hz,1H),4.37(s,2H),4.16(t,J＝6.5Hz,2H),2.28(m,2H),1.62-1.68(m,2H),1.40-1.45(m,4H),1.26-1.39(m,6H),0.95(t,J＝7.5Hz,3H),0.89(t,J＝6.5Hz,3H).13C NMR(125MHz,CDCl3):δ＝166.53,145.63,144.03,134.75,115.80,63.21,55.98,30.60,29.76,28.23,27.95,27.61,21.54,18.17,13.04,12.72.HR-MS(ESI):m/z calculated for C16H28O3[M+H]+:269.2111,found:269.2105.FTIR(KBr,cm-1):3667.55,3592.70,3673.42,2969.15,2924.77,2354.70,1698.72,1311.46,1173.28,1088.65,1049.63,880.78.
实施例29：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(15.9mg，收率22％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.24(d,J＝16.5Hz,1H),5.91(t,J＝7.5Hz,1H),5.83(t,J＝15.5Hz,1H),4.15(t,J＝7.0Hz,2H),3.66(t,J＝6.5Hz,2H),2.34(t,J＝7.5Hz,2H),2.20(m,2H),1.63-1.68(m,4H),1.39-1.45(m,4H),1.30-1.31(m,4H),0.95(t,J＝7.5Hz,3H),0.89(t,J＝6.5Hz,3H).13CNMR(125MHz,CDCl3):δ＝166.74,147.60,142.14,135.59,114.23,63.15,61.49,30.55,30.54,29.80,27.85,27.68,21.75,21.51,18.18,12.99,12.73.HR-MS(ESI):m/z calculated for C17H30O3[M+H]+:283.2268,found:283.2264.FTIR(KBr,cm-1):3383.11,2973.09,2925.40,2899.49,1454.95,1381.99,1087.75,880.42.
实施例30：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到白色固体产物(100.9mg，收率82％)。
核磁共振谱图分峰如下：1H NMR(400MHz,CDCl3):δ＝7.28(d,J＝16.4Hz,1H),6.05(t,J＝7.6Hz,1H),5.82(d,J＝16.0Hz,1H),4.15(t,J＝6.8Hz,2H),3.69-3.74(m,1H),3.64(t,J＝6.8Hz,2H),2.36-2.48(m,2H),2.24(q,J＝7.2Hz,2H),1.63-1.69(m,2H),1.56-1.58(m,2H),1.48-1.50(m,4H),1.40(q,J＝7.2Hz,4H),1.31-1.33(m,14H),0.95(t,J＝7.6Hz,3H),0.88(t,J＝5.2Hz,3H).13C NMR(125MHz,CDCl3):δ＝166.54,147.74,144.31,132.70,114.88,69.50,63.22,62.00,36.33,33.91,31.73,30.81,29.78,28.38,28.32,28.27,28.17,28.15,24.80,24.67,21.60,18.18,13.07,12.73.HR-MS(ESI):m/zcalculated for C25H46O4[M+Na]+:411.3469,found:411.3468.FTIR(KBr,cm-1):3564.43,3416.76,2970.62,2925.50,1633.49,1621.48,1462,81,1393.77,1048.78.
实施例31：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到白色固体产物(88.1mg，收率67％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.20(d,J＝16.0Hz,1H),5.96(t,J＝7.5Hz,1H),5.75(d,J＝16.0Hz,1H),4.07(td,J＝1.0Hz,J＝6.5Hz,2H),3.62-3.64(m,1H),3.59(s,3H),2.30-2.40(m,2H),2.23(t,J＝6.5Hz,2H),2.17(q,J＝7.5Hz,2H),1.53-1.59(m,4H),1.32-1.36(m,4H),1.18-1.24(m,16H),0.87(t,J＝7.5Hz,3H),0.82(t,J＝6.5Hz,3H).13CNMR(125MHz,CDCl3):δ＝173.27,166.57,147.80,144.15,132.83,114.86,69.48,63.21,50.45,36.33,33.95,33.03,30.82,29.78,28.33,28.15,28.10,29.07,28.00,24.82,23.86,21.60,18.18,13.07,12.73.HR-MS(ESI):m/z calculated forC26H46O5{[M-H2O]+H}+:421.3318,found:421.3326.FTIR(KBr,cm-1):3583.23,3456.28,1842.15,1773.28,1428.16,1422,86,1360.65,1337.42.
实施例32：
取干净反应瓶，加入小磁子，烘干，加入乙酸钯(6.7mg,0.03mmol,10mol％)、N-乙酰-L-苯丙氨酸(31.0mg,0.15mmol,50mol％)、碳酸银(124.1mg,0.45mmol,1.5当量)、碳酸铯(29.3mg,0.09mmol,30mol％)、三氟乙醇(217μL,3.0mmol,10.0当量)、1,4-二恶烷(0.6mL),再加入相应的烯基醇(0.3mmol,1.0当量)和缺电子烯烃(0.6mmol,2.0当量)。然后，在氩气下70℃加热反应16小时后，反应液经直接柱层析分离后得到黄色油状产物(86.8mg，收率61％)。
核磁共振谱图分峰如下：1H NMR(500MHz,CDCl3):δ＝7.07(dd,J＝17.5Hz,J＝22.5Hz,1H),5.99(t,J＝7.5Hz,1H),5.60(t,J＝18.0Hz,1H),4.05-4.09(m,4H),3.66-3.68(m,4H),2.41(dq,J＝8.5Hz,J＝14.0Hz,2H),2.29(t,J＝7.5Hz,2H),2.22(q,J＝7.5Hz,2H),1.61(t,J＝7.0Hz,3H),1.25-1.34(m,23H),0.88(t,J＝7.0Hz,3H).13C NMR(125MHz,CDCl3):δ＝173.27,151.77(d,JC-P＝6.3Hz),143.63,133.07(d,JC-P＝22.5Hz),110.04(d,JC-P＝190.0Hz),69.52,60.68,60.64,50.46,36.36,33.61,33.03,30.79,28.30,28.13,28.05,28.00,24.81,23.86,21.59,15.41,15.36,13.05.HR-MS(ESI):m/zcalculated for C25H47O6P[M+H]+:475.3183,found:475.3203.FTIR(KBr,cm-1):3564.02,3383.12,1738.33,1645.99,1625.66,1534.89,1621.55,1416.88,1242.32,1027.57,963.56.
Claims (3)
1.一种醇取代的(E,E)-构型的枝型共轭二烯衍生物的合成方法，其特征在于，将烯基醇化合物、缺电子烯烃、过渡金属盐催化剂、配体、氧化剂以及碱与添加剂置于有机溶剂中，于惰气氛围下加热反应，得到式I、式II或式III所示结构的化合物；
所述烯基醇化合物为如式V所示的取代2-烯丙醇、如式IV所示的取代3-烯丁醇或如式VI所示的取代4-烯戊醇；
所述缺电子烯烃为如式VII、式VIII或式IX所示的丙烯酸酯、取代苯乙烯、取代丙烯酰胺或烯基膦酸酯：
式I和式IV中，R1为C1～8烷基、酯基取代的C1～8烃基、C1～8羟烃基或C6～10芳基；R2为H、甲基或与R1连接成五元环、六元环；R3为H、环烷基、含氧杂环、C1～6烷基、烯基、联苯基或取代芳基；所述的取代芳基的取代基为C1～6的烷基、C1～6的烷氧基或卤素；
式I和式VII中R4为酯基、酮羰基、芳基、酰胺基、膦酸酯基；
式II和式V中R5为C1～6烷基；R6为H或C1～3烷基；
式II和式VIII中R7为C1～6酯基；
式III和式VI中R8为C1～8烷基；
式III和式IX中R9为C1～6酯基；
所述过渡金属盐催化剂为醋酸钯；所述配体为N-乙酰-L-苯丙氨酸；所述的氧化剂为碳酸银；所述碱为碳酸铯；所述的添加剂为三氟乙醇；所述有机溶剂为1,4-二恶烷。
2.根据权利要求1所述的合成方法，其特征在于，所述烯基醇化合物：缺电子烯烃：过渡金属盐催化剂：氨基酸配体：氧化剂：碱：添加剂的物质的量之比为1：1～2：0.05～0.15：0.2～0.8：1.0～2.0：0.2～0.5：5～15。
3.根据权利要求1所述的合成方法，其特征在于，所述有机溶剂的体积用量以烯基醇化合物的物质的量计为3～5L/mol；所述加热反应温度为50～100℃，反应时间16～24小时。
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