CN113480419B - 一种合成α，β不饱和酮的方法 - Google Patents

一种合成α，β不饱和酮的方法 Download PDF

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CN113480419B
CN113480419B CN202110602417.5A CN202110602417A CN113480419B CN 113480419 B CN113480419 B CN 113480419B CN 202110602417 A CN202110602417 A CN 202110602417A CN 113480419 B CN113480419 B CN 113480419B
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刘妙昌
缪威航
吴键
周云兵
吴华悦
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Abstract

本发明属于化学合成技术领域，具体涉及一种合成α，β不饱和酮的方法。该反应采用Co(acac)2或Co(acac)3、配体和AlMe3的协同催化体系，提供了一个原子经济和选择性合成α，β不饱和酮的途径，产率高，且具有底物范围广的优点。

Description

一种合成α，β不饱和酮的方法
技术领域
本发明属于化学合成技术领域，具体涉及一种合成α， β不饱和酮的方法。
背景技术
在过渡金属催化的炔与醛的氢化反应是一种很有前途的合成α,β-不饱和酮的策略，主要是由于它的高原子经济和容易获得的原料仍需解决的关键问题之一是避免由于关键酰基金属中间体在分子间加氢酰化过程中固有的不稳定性而引起的醛脱羰的发生。在这方面，已经建立了大量螯合控制的铑催化炔烃氢酰化方法，这些方法依赖于使用含有多种导向基团的醛，如P-，O-，N-。这些螯合基团的存在使酰基金属中间体稳定，从而有效抑制了不需要的脱羰副产物的的形成，具有底物范围广、反应条件温和的优点。但是，与去除导向基团和使用贵重Rh催化剂有关的问题削弱了它的整体吸引力。过渡金属催化炔烃氢酰化的非螯合控制方法目前还不多，但存在催化剂价格昂贵、底物范围窄、选择性差、产率低等问题。
另一方面，在过去的几十年里，化学家们一直在追求第一行过渡金属催化反应的发展。钴由于其低成本和高丰度的特点，是包括铱和铑在内的贵重过渡金属的一个有吸引力的和互补的替代品，它在催化氢化、氢甲酰化和氢乙烯化等有价值的反应中也取得了重大突破。经检索，目前还没有关于钴催化选择性分子间炔氢化反应的催化体系。
发明内容
本发明的目的是为了克服现有技术存在的缺点和不足，而提供一种合成α， β不饱和酮的方法。
本发明所采取的技术方案如下：一种合成α， β不饱和酮的方法，其反应式为：
；
其中R1为芳香取代基或脂肪取代基；
所述芳香取代基为苯环、卤素取代的苯环、中性基团取代的苯环、对位和/或间位富电子基团取代的苯环、邻位甲基取代的苯环、萘环或含取代基的萘环、呋喃环或含取代基的呋喃环、噻吩环或含取代基的噻吩环、吲哚环或含取代基的吲哚环中的一种；
其中R2为芳香基团或脂肪基团；
R3为芳香基团或脂肪基团；
反应采用Co(acac)2或Co(acac)3、配体和AlMe3的协同催化体系；
所述配体为dppe、dppb、dppp、L1、L2、L3中的一种，配体的化学式具体为以下：
。
优选的，R2和R3为相同的基团。
优选的，反应采用Co(acac)3。
优选的，反应采用dppp作为配体。
优选的，反应在120-160℃下进行。
优选的，反应在氮气氛围下进行。
本发明的有益效果如下：本发明提出了利用Co/LA协同C-H活化的策略，提供了一个原子经济和选择性合成α， β不饱和酮的途径，产率高，且具有底物范围广的优点。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚，下面将对本发明作进一步地详细描述。
实施例1：
选择苯甲醛1和二丁基乙炔2作为模板底物，筛选出最优反应条件，反应式如下所示，反应条件控制和收率如表1所示，以Co(acac)3为催化剂，dppp为配体，MAD为路易斯酸，在三甲苯中，120 ℃，12h，模型反应氢化产物(3)的产率仅为10%(反应 1)。由于Lewis酸在反应中的重要作用，产品的产率与Lewis酸密切相关。为此，我们尝试筛选其他路易斯酸(反应2和反应3)，发现使用AlMe3作为路易斯酸可使收率达到60%，E/ Z立体选择性达到完全水平。对照实验表明，路易斯酸对反应至关重要(反应4)。接下来，考察催化剂作为反应的另一个关键因素。3催化剂生产所需的产品产量下降(反应5)。没有观察到使用CoCl2或转换CoI2(反应6和7)。收益率可能会进一步提高,提高反应温度到160 ℃(反应8和9)。为配体的选择,功能化的dppp被证明不如未取代的dppp(反应10-13)。其他配体包括dppe和dppb也有效，尽管产量不高(反应14和15)。此外，我们发现先前的共催化1,3-二烯氢化反应条件11与炔氢化反应完全不相容(反应16)。
。
表1 合成α， β不饱和酮的反应条件的优化
a 反应条件: 1 (0.3 mmol), 2 (0.45 mmol), Co (5 mol%), 配体 (10 mol%),LA (30 mol%), 均三甲苯 (2.0 mL), 在N2气氛下，反应5 h，分离产率。 b 1 (0.3 mmol), 2(0.45 mmol), CoI2 (5 mol%), L2 (5 mol%), In (10 mol%), InBr3 (5 mol%), DCE(0.5 mL), 160 °C, 24 h, 分离产率。
实施例2：
以实施例1优化后的最优反应条件（Co(acac)3 (5.0 mol%), dppp (10.0 mol%)，均三甲苯 (2.0 mL)，AlMe3 (30.0 mol%)，醛类化合物1 (0.3 mmol)，炔类化合物2 (0.45mmol, 1.5 equiv)）进行底物的拓展，拓展结果如表2所示。
从表2中可以看出，在最优反应条件下(4- 8,12 -21)，各种含卤素、中性基团和对位或间位富电子基团的苯甲醛衍生物反应良好。苯甲醛上的酯(8)和硝基(9)等退电子取代基的存在导致了反应效率的显著降低。含活性氢的芳香醛如4-羟基苯甲醛(10)和4-氨基苯甲醛(11)在标准条件下无反应性。可能是由于空间体的原因，该钴基催化体系除2-甲基苯甲醛(22)外，没有催化邻位取代苯甲醛(23和24)的反应。当使用2-萘醛作为底物时，分离出产物(25)的中等产量。十二-5-炔与含有呋喃(26)、噻吩(27)和吲哚环(28)的醛偶联，分别获得了72%、84%和46%的杂芳β、γ-不饱和酮。值得注意的是，除了芳香族醛外，脂肪族醛在以前的加氢酰化中是一类具有挑战性的底物，它们与炔(2)能很好地反应生成脂肪族β、γ-不饱和酮(29-33)。
然后对炔组分的范围进行了评估，选择了苯甲醛作为偶联伙伴。其他对称的脂肪族炔包括己-3-炔和十二-6-炔被证明是合适的底物(34和35)。不对称脂肪族炔烃的使用导致同分异构体的区域比例为1:1(36和37)的混合物。对称芳香炔也被成功地应用，虽然E/ Z立体选择性中等(38-41)，但相应的产物的产率为43%-48%。
表2 底物拓展结果
。
综上所述，采用本发明所限定的协同催化体系可以以较高收率获得α， β不饱和酮，且底物范围广。
其中，以最优合成条件为例，上述实施例中的各反应的具体反应步骤如下：
。
在装有搅拌磁子10 mL 压力管(Scheme 4-12)中加入Co(acac)3 (5.0 mol%),dppp (10.0 mol%)，然后抽真空换氮气各三次，在氮气氛围下，将均三甲苯 (2.0 mL)，AlMe3 (30.0 mol%)，醛类化合物1 (0.3 mmol)，炔类化合物2 (0.45 mmol, 1.5 equiv)加入压力管，反应混合物在160 ℃下反应18 h。反应结束后，冷却至室温，减压浓缩。通过硅胶柱层析法纯化，以乙酸乙酯和石油醚为洗脱剂，分离得到产物。
以上所揭露的仅为本发明较佳实施例而已，当然不能以此来限定本发明之权利范围，因此依本发明权利要求所作的等同变化，仍属本发明所涵盖的范围。

Claims (6)

1.一种合成α， β不饱和酮的方法，其特征在于：其反应式为：
；
其中R1为芳香取代基或脂肪取代基；
所述芳香取代基为3,4-二甲氧基取代的苯环、3-甲氧基取代的苯环、3-卤素取代的苯环、2-甲基取代的苯环、2,4,6-三甲基取代的苯环、2-甲氧基取代的苯环、萘环或含取代基的萘环、呋喃环或含取代基的呋喃环、噻吩环或含取代基的噻吩环、吲哚环或含取代基的吲哚环中的一种；
其中R2为芳香基团或脂肪基团；
R3为芳香基团或脂肪基团；
反应采用Co(acac)2或Co(acac)3、配体和AlMe3的协同催化体系；
所述配体为dppe、dppb、dppp、L1、L2、L3中的一种，配体的化学式具体为以下：
。
2.根据权利要求1所述的合成α， β不饱和酮的方法，其特征在于：R2和R3为相同的基团。
3.根据权利要求1所述的合成α， β不饱和酮的方法，其特征在于：反应采用Co(acac)3。
4.根据权利要求1所述的合成α， β不饱和酮的方法，其特征在于：反应采用dppp作为配体。
5.根据权利要求1所述的合成α， β不饱和酮的方法，其特征在于：反应在120-160℃下进行。
6.根据权利要求1所述的合成α， β不饱和酮的方法，其特征在于：反应在氮气氛围下进行。
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