CN114380679B - 一种钯催化氧化耦联的方法 - Google Patents

一种钯催化氧化耦联的方法 Download PDF

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CN114380679B
CN114380679B CN202011117880.2A CN202011117880A CN114380679B CN 114380679 B CN114380679 B CN 114380679B CN 202011117880 A CN202011117880 A CN 202011117880A CN 114380679 B CN114380679 B CN 114380679B
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陈庆安
赵朝阳
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Abstract

本发明涉及一种钯催化氧化耦联的方法。具体为，以1‑四氢萘酮，异戊烯醇为原料，在卡宾钯催化的条件下，实现酮和异戊烯醇的氧化耦联。本发明有以下优点，异戊烯醇直接作为耦联试剂，选择性实现氧化耦联，广泛的底物范围，很好的收率，同时具有很好地Z/E选择性。

Description

一种钯催化氧化耦联的方法
技术领域
本发明涉及一种钯催化氧化耦联的方法。具体为，以1-四氢萘酮，异戊烯醇为原料，在卡宾钯催化的条件下，实现酮和异戊烯醇的氧化耦联。本发明有以下优点，异戊烯醇直接作为烷基化试剂，选择性实现氧化耦联，广泛的底物范围，很好的收率，同时具有很好地Z/E选择性。
背景技术
羰基是天然产物中常见的官能团，也广泛存在于在前200种处方药物中。并且醇类作为天然产品和工业上丰富的原料，具有绿色廉价的优点，是一种很好的偶联试剂。在过去的这些年中，醇类主要作为烷基化试剂和烯丙基化的原料，如：Pd催化的Tsuji烯丙基化反应合成α-烯丙基酮产物 (式1)。
通过文献检索发现(式1)，张万斌小组在2014年独立地报道了通过烯丙基氯化钯催化合成α-烯丙基酮产物的方法(Huo,G.Yang,D.Liu,Y.Liu,I. Gridnev,*and W.Zhang*X.Zhao,D.Liu,H.Guo,Y.Liu,W.Zhang,Angew. Chem.Int.Ed.2014,53,6776.)。上述方法的成功取决于π-烯丙基钯配合物的生成，属于Tsuji烯丙基化反应的一种，得到直接耦联的产物。相比之下，实现他们之间的氧化耦联同样十分重要。
Figure BDA0002730968860000011
发明内容
本发明目的在于以酮和异戊烯醇为原料，在钯卡宾催化的条件下，快速实现酮和醇之间的氧化耦联，具有很好的收率，同时具有很好地Z/E选择性。
本发明是通过以下技术方案实现的：
一种钯催化氧化耦联的方法，
以酮和异戊烯醇为原料，在钯卡宾催化的条件下，以很好的收率快速实现酮α位的氧化耦联。反应式如下所示：
Figure BDA0002730968860000021
具体操作步骤如下：
在氩气或氮气气氛下，于反应器中加入烯丙基氯化钯，卡宾盐，甲醇钠/乙醇钠，无水甲苯溶剂，室温下搅拌反应1h，随后加入酮与异戊烯醇，反应生成目标产物3。点板监测反应体系，反应结束后，旋干溶剂，柱层析流动相：石油醚/***(体积比)；
反应物酮上取代基R1可以是苯基、3-甲氧基苯基、4-甲氧基苯基、5- 甲氧基苯基、3-甲基苯基、以及3-氟苯基中的一种、二种、三种或四种；反应物酮亚氨基酸酯取代基R2可以是甲基、乙基、苯基以及苄基中的一种、二种、三种或四种。
所用金属铜盐为下述中的一种或二种以上：烯丙基氯化钯、氯化钯、醋酸钯、三氟乙酸钯、肉桂基氯化钯以及二(乙酰丙酮)钯。其中，钯盐与酮的摩尔比为0.001-1，优选范围为0.01-0.2。
所用卡宾盐试剂为下述中的一种或二种以上：L1、L2、L3、L4、L5、 L6，(结构式如下)卡宾盐试剂与与酮的摩尔比为0.001-1，优选范围为 0.01-0.2。
Figure BDA0002730968860000022
所用溶剂为，以甲醇、乙醇、异丙醇、叔丁醇、乙腈、甲苯、氯苯、对甲氯苯、环己烷、四氢呋喃、2-甲基四氢呋喃、乙二醇二甲醚、甲基叔丁基醚、二氯甲烷、二氯乙烷、1,4-二氧六环、乙酸乙酯、N,N-二甲基甲酰胺、 N-甲基吡咯烷酮、二甲亚砜中的一种或二种以上为溶剂，溶剂优选甲苯、四氢呋喃、1,4-二氧六环、二氯乙烷中的一种或两种，1-四氢萘酮于溶剂中优选浓度范围0.01-1.5mol/L。
异戊烯醇用量是摩尔量的0.5-10倍之间，优选2-5倍之间。
有机胺为苯胺、环己胺、哌啶和/或四氢吡咯，有机胺与酮的摩尔比为 0.1-3.0，优选范围为0.2-1.0；反应温度为70℃条件；反应时间在0.5-36h 之间，优选反应时间16-24h。
本发明具有如下优点：
本发明有以下优点，金属钯盐和卡宾盐在碱条件下原位制备卡宾钯；异戊烯醇直接作为耦联试剂，选择性实现氧化耦联，广泛的底物范围，很好的收率。同时具有很好地Z/E选择性。(如果烯烃的双键有一定的构型，则应用Z/E对双键的构型进行标记，Z就是烯烃双键碳上两个大的基团在一边，另外两个小的基团在另一边，同样E就是一个烯碳上大的基团和另一个烯碳上小的基团在一边。)
附图说明
图1为化合物3a的1H NMR和13C NMR图；
图2为化合物3b的1H NMR和13C NMR图；
图3为化合物3c的1H NMR和13C NMR图；
图4为化合物3d的1H NMR和13C NMR图；
图5为化合物3e的1H NMR和13C NMR图；
图6为化合物3f的1H NMR，13C NMR和19F NMR图；
图7为化合物3g的1H NMR和13C NMR图；
图8为化合物3h的1H NMR和13C NMR图；
图9为化合物3i的1H NMR和13C NMR图；
具体实施方式
下面将以具体的实施例来对本发明加以说明，但本发明的保护范围不局限于这些实例。
1.钯卡宾催化酮α位氧化耦联的反应
在氮气气氛下，在2.0mL封管中，依次加入烯丙基氯化钯(相对于酮量的2.5mol％,1.8mg)，卡宾盐试剂L(相对于酮量的5mol％)，有机碱(相对于酮量的3.0equiv.)，氯苯1mL，室温下搅拌反应1h，随后加入1-四氢萘酮(0.20mmol,29.2mg)，有机胺(0.10mmol)和异戊烯醇(0.30mmol,25.8 mg)，70℃反应16h，结束后加入均三甲基苯作为内标，GC-FID检测目标产物收率。
Figure BDA0002730968860000041
表1.催化剂、溶剂对反应的影响
Figure BDA0002730968860000042
Figure BDA0002730968860000051
2.底物类型
在2.0mL封管中，依次加入烯丙基氯化钯(2.5mol％,1.8mg)，卡宾盐 L5(5mol％)，甲醇钠(3.0equiv.,32.4mg)，氯苯1mL，室温下搅拌反应1h，随后加入酮(0.20mmol,29.2mg)，哌啶(0.10mmol,8.6mg)和异戊烯醇 (0.30mmol,25.8mg)，70℃反应16h，结束后旋干，柱层析分离，流动相为石油醚/乙酸乙酯(体积比20:1)可得到目标产物3a。
Figure BDA0002730968860000052
Figure BDA0002730968860000053
Figure BDA0002730968860000061
Figure BDA0002730968860000062
1H),7.45(td,J＝7.4,1.5Hz,1H),7.33(td,J＝7.6,1.2Hz,1H),7.24(t,J＝7.1Hz,1H),6.23(dt,J＝12.2,1.5Hz,1H),3.01–2.83(m,4H),1.98(s,3H),1.95(s,3H).13C NMR(101MHz,CDCl3)δ187.8,147.3,143.4,134.0,132.8,132.3,131.5,128.1,128.0,126.8,120.9,28.8,27.2,25.4,19.1.HRMS calculated for C15H16O[M+H]+213.1274,found 213.1274.
Figure BDA0002730968860000071
6.33–6.15(m,1H),3.13(h,J＝6.3Hz,1H),2.90(dd,J＝14.7,4.3Hz,1H),2.79(dd,J＝14.8,5.6Hz,1H),1.98(s,3H),1.96(s,3H),1.29(d,J＝7.0Hz,3H).13C NMR(100MHz,CDCl3)δ187.8,148.5,147.3,133.5,133.0,130.0,128.2,126.9,126.8,120.9,33.1,32.9,27.2, 22.0,19.1.HRMS calculated for C16H18O[M+H]+227.1430,found 227.1426
Figure BDA0002730968860000072
1H),7.14(d,J＝8.3Hz,1H),7.03(dd,J＝8.3,2.9Hz,1H),6.27–6.19(m,1H),3.85(s,3H),2.92–2.81(m,4H),1.98(s,3H),1.95(s,3H).13C NMR(101MHz,CDCl3)δ187.7,158.5,147.1,136.1,134.8,132.3,131.5,129.3,121.0,120.8,110.3,55.5,27.9,27.2,25.6,19.1.HRMS calculated for C16H18O2[M+H]+243.1380,found 243.1382
Figure BDA0002730968860000073
1H),6.85(dd,J＝8.7,2.6Hz,1H),6.70(d,J＝2.5Hz,1H),6.22(dt,J＝12.1,1.5Hz,1H),3.86(s,3H),2.99–2.81(m,4H),1.97(s,3H),1.94(s,3H).13C NMR(101MHz,CDCl3)δ 186.8,163.2,146.6,145.9,131.6,130.5,128.4,127.5,120.9,113.1,112.3,55.4,29.2,27.2,25.5,19.1.HRMS calculated for C16H18O2[M+H]+243.1380,found 243.1383
Figure BDA0002730968860000074
J＝12.1,1.6Hz,1H),7.32–7.22(m,1H),7.12(d,J＝7.7Hz,1H),6.23(dt,J＝12.2,1.4Hz,1H),2.94–2.82(m,4H),2.37(s,3H),1.98(s,3H),1.94(s,3H).13C NMR(101MHz,CDCl3) δ188.0,147.0,140.6,136.5,133.8,133.7,132.1,131.8,128.2,128.0,121.0,28.4,27.2,25.6, 21.0,19.1.HRMS calculated for C16H18O[M+H]+227.1430,found 227.1437
Figure BDA0002730968860000081
7.69(d,J＝12.1Hz,1H),7.22(dd,J＝8.4,5.2Hz,1H),7.15(td,J＝8.3,2.8Hz,1H),6.23(dt,J＝12.3,1.6Hz,1H),2.97–2.79(m,4H),1.98(s,3H),1.96(s,3H).13C NMR(101 MHz,CDCl3)δ186.8(d,J＝1.9Hz),161.8(d,J＝245.7Hz),148.0,139.1(d,J＝2.9Hz), 135.6(d,J＝6.3Hz),133.0,130.7(d,J＝0.9Hz),129.8(d,J＝7.0Hz),120.9,119.9(d,J＝22.1Hz),114.0(d,J＝22.0Hz),28.0,27.2,25.4,19.1.19F NMR(376MHz,CDCl3)δ-115.2.HRMS calculated for C15H15FO[M+H]+231.1180,found 231.1180
Figure BDA0002730968860000082
1.98(s,3H),1.96(s,3H).13C NMR(100MHz,CDCl3)δ194.2,149.0,148.8,139.4,134.1,133.4,129.7,127.3,126.2,124.0,122.1,30.3,27.1,19.2.HRMS calculated for C14H14O[M+H]+199.1117,found 199.1121
Figure BDA0002730968860000083
1.98(s,3H),1.96(s,3H).13C NMR(101MHz,CDCl3)δ194.3,148.5,146.4,139.6,137.3,135.3,134.0,129.5,125.9,124.1,122.1,29.9,27.1,21.2,19.2.HRMS calculated forC15H16O[M+H]+213.1274,found 213.1279.
Figure BDA0002730968860000084
Hz,1H),6.20(d,J＝12.1Hz,1H),2.76(t,J＝6.9Hz,2H),2.43(t,J＝6.8Hz,2H),1.97(s,3H),1.94(s,3H),1.90(t,J＝6.9Hz,2H).13C NMR(101MHz,CDCl3)δ198.4,147.3,139.5,139.4,134.9,133.0,132.0,128.9,128.8,126.8,120.7,31.3,27.2,26.4,24.1,19.1.HRMScalculated for C16H18O[M+H]+227.1430,found 227.1437
Figure BDA0002730968860000085
在2.0mL小瓶，依次加入Pd/C(Pd质量含量5％,4mg)，溶剂甲醇1mL，放入高压釜中，通入氢气，压力位500psi，50℃反应16h，结束后旋干，柱层析分离，流动相为石油醚/乙酸乙酯(体积比1：0)可得到目标产物4，产率为95％，76.8mg。

Claims (15)

1.一种钯催化氧化耦联的方法，其特征在于：
酮和异戊烯醇在钯卡宾试剂的作用下，可以实现酮和异戊烯醇的氧化耦联；
具体操作步骤如下：
在氩气和/或氮气气氛下，于反应器中加入金属钯盐，卡宾盐，有机碱，溶剂，室温下搅拌反应1h以上，随后加入酮与异戊烯醇，有机胺，反应生成目标产物；
反应式如下所示：
Figure DEST_PATH_IMAGE001
；
反应物酮式1上无取代基或者取代基R可以是4-甲基、6-甲基、7-甲基、5-甲氧基、6-甲氧基苯基、7-甲氧基苯基、以及7-氟中的一种、二种、三种或四种；
有机碱为甲醇钠、乙醇钠、叔丁醇钠、叔丁醇钾、叔丁醇锂中的一种或二种以上；所用卡宾盐试剂为下述中的一种或二种以上：L1、L2、L4、L5结构式如下所示；
Figure 764248DEST_PATH_IMAGE002
。
2.根据权利要求1所述的方法，其特征在于：
点板监测反应体系，反应结束后，旋干溶剂，柱层析流动相：体积比50:1-10:1的石油醚/***。
3.根据权利要求1所述的方法，其特征在于：
所用金属钯盐为下述中的一种或二种以上：烯丙基氯化钯、氯化钯、醋酸钯、三氟乙酸钯、肉桂基氯化钯或二(乙酰丙酮)钯；其中，钯盐与酮的摩尔比为0.001-1。
4.根据权利要求3所述的方法，其特征在于：
其中，钯盐与酮的摩尔比为0.01-0.2。
5.根据权利要求1所述的方法，其特征在于：
卡宾盐试剂与酮的摩尔比为0.001-1。
6.根据权利要求5所述的方法，其特征在于：
卡宾盐试剂与酮的摩尔比为0.01-0.2。
7.根据权利要求1所述的方法，其特征在于：
所用溶剂为甲醇、乙醇、异丙醇、叔丁醇、乙腈、甲苯、氯苯、对甲氯苯、环己烷、四氢呋喃、2-甲基四氢呋喃、乙二醇二甲醚、甲基叔丁基醚、二氯甲烷、二氯乙烷、1,4-二氧六环、乙酸乙酯、N,N-二甲基甲酰胺、N-甲基吡咯烷酮、二甲亚砜中的一种或二种以上；
酮于溶剂中浓度范围0.01-1.5 mol/L。
8.根据权利要求7所述的方法，其特征在于：
所用溶剂为甲苯、四氢呋喃、1,4-二氧六环、二氯乙烷中的一种或两种以上。
9.根据权利要求1所述的方法，其特征在于：
异戊烯醇用量是酮摩尔量的0.5-10倍之间；
加入酮和异戊烯醇、 有机胺之后的反应温度为20-100 oC，反应时间在0.5-36 h之间。
10.根据权利要求9所述的方法，其特征在于：
异戊烯醇用量是酮摩尔量的2-5倍之间；
加入酮和异戊烯醇、 有机胺之后的反应温度为40-70 oC，反应时间在16-24h之间。
11.根据权利要求1所述的方法，其特征在于：
有机胺为苯胺、环己胺、哌啶或四氢吡咯中的一种或二种以上，有机胺与酮的摩尔比为0.1-3.0。
12.根据权利要求11所述的方法，其特征在于：
有机胺与酮的摩尔比为0.2-1.0。
13.根据权利要求1所述的方法，其特征在于：
有机碱与酮的摩尔比为0.1-5.0。
14.根据权利要求13所述的方法，其特征在于：
有机碱与酮的摩尔比为1.0-3.0。
15.根据权利要求1所述的方法，其特征在于：酮为1-四氢萘酮。
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Citations (3)

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Publication number Priority date Publication date Assignee Title
DD293805A5 (de) * 1990-04-26 1991-09-12 Adw,Forschungsstelle F. Chemische Toxikologie,De Verfahren zur herstellung substituierter 2-(5-oxo-pent-2-en-1-yliden)-indan-1-one
WO2016013976A1 (en) * 2014-07-23 2016-01-28 Nanyang Technological University Method of forming a multi-substituted benzene compound
CN110790649A (zh) * 2019-11-07 2020-02-14 西北大学 一种合成多取代α,β不饱和酮的方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD293805A5 (de) * 1990-04-26 1991-09-12 Adw,Forschungsstelle F. Chemische Toxikologie,De Verfahren zur herstellung substituierter 2-(5-oxo-pent-2-en-1-yliden)-indan-1-one
WO2016013976A1 (en) * 2014-07-23 2016-01-28 Nanyang Technological University Method of forming a multi-substituted benzene compound
CN110790649A (zh) * 2019-11-07 2020-02-14 西北大学 一种合成多取代α,β不饱和酮的方法

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Palladium-Catalyzed Allylic Alkylation of Simple Ketones with Allylic Alcohols and Its Mechanistic Study;HUo Xiaohong等;《Angewandte Chemie International Edition》;20140521;第53卷;全文 *

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