general摘要
过渡金属催化的交叉偶联反应作为一种高效构建碳碳键及碳杂键的工具，已成为了有机合成化学中的一种最具吸引力且功能多样的合成方法。过渡金属特别是金属钯因为高效性和高选择性的反应特性，备受合成化学家的推崇。钯催化的交叉偶联反应已从基础研究逐步走向应用研究，如功能材料、天然产物及药物中间体的合成。其中，化学研究者借助钯催化烯丙基羧酸酯的偶联反应合成了各式各样的有机分子。因此，本论文发展了两例钯催化的基于烯丙基羧酸酯的交叉偶联反应：
第一章是文献综述，阐述了烯丙基羧酸酯在合成化学中的反应特性、钯催化的基于烯丙基羧酸酯烯丙位的偶联反应和钯催化的基于烯丙基羧酸酯碳碳双键的偶联反应。
第二章是钯催化的烯丙基炔酸酯与异腈的偶联反应。我们成功地实现了烯丙基炔酸酯与异腈的交叉偶联，得到了一系列的1,4-烯炔-3-酮化合物。该反应具有反应条件温和与良好的官能团容忍性的优点。反应机理表明，反应是通过金属钯活化烯丙基炔酸酯的碳氧单键，再经过分子内脱羧形成炔基烯丙基钯中间体，继而与异腈进行交叉偶联反应。
第三章为钯催化的烯丙基羧酸酯、降冰片烯与联硼酸酯三组分串联反应。我们在课题组前期工作的基础之上，以Pd(PPh3)4为催化剂，以Zn(OTf)2为路易斯酸，在丙醇溶剂中实现了烯丙基羧酸酯、降冰片烯与联硼酸酯三组分的偶联反应，高效地一步构建了C(sp3)-C(sp3)键和C(sp3)-B键。该反应具有很好的化
学选择性和区域选择性，以及良好的底物适用性。
关键词：钯催化；烯丙基羧酸酯；烯丙基炔酸酯；交叉偶联反应；异腈；降冰片烯；联硼酸酯
Abstract
Transition metal-catalyzed cross-coupling reaction have emerged as a powerful tool for the efficient construction of carbon-carbon and carbon-heteroatom bonds, hence, have become the most attractive and versatile methods in organic synthesis chemistry. Transition metals especially palladium are respected by synthetic chemists becau of high efficiency and high lectivity in organic reactions. Palladium-catalyzed cross-coupling reactions have shifted from basic rearch to practical aspects gradually, such as functional materials, natural products and pharmaceutical intermediates. Chemical rearchers have synthesized a wide variety of organic molecules via palladium-catalyzed coupling reaction of allyl carboxylates. In this paper, two palladium-catalyzed cross-coupling reactions bad on allyl carboxylates were developed:
yell是什么意思In Chapter 1, the reaction characteristics of allyl carboxylates in synthetic chemistry, palladium-catalyzed coupling reaction bad on the allylic position of allyl carboxylates and palladium-catalyzed coupling reaction of carbon-carbon double bonds of allyl carboxylates were introduced.
In Chapter 2, palladium-catalyzed coupling reaction of allyl alkynoates with isocyanides is described. We have achieved the cross-coupling of allyl alkynoates with isocyanides as a ries of 1,4-enyne-3-ones were obtained. This approach shows advantages of mild reaction conditions and excellent functional group compatibility. The mechanism shows that the reaction is through the activation of C-O bond of allyl alkynoates by metal palladium, and then the intramolecular decarboxylation to form alkynyl allyl palladium intermediates, followed by cross-coupling reaction with isonitriles.
In Chapter 3, palladium-catalyzed tandem reaction of allyl carboxylates, norbornenes and diboronates is described. Combining with the preliminary work of our group, we developed a three-component coupling reaction of allyl alkanoates, norbornenes and diboronates in the condition of Pd(PPh3)4 as cataly, Zn(OTf)2as
C(sp3)-C(sp3) bond and a C(sp3)-B bond in a single reaction. The reaction have good chemolectivity and regiolectivity, and good substrate suitability.
Keywords: palladium-catalyzed; allyl carboxylates; allyl alkynoates; cross-coupling reaction; isocyanides; norbornenes; diboronates
目录
audience复数摘要...................................................................................................................... I ABSTRACT .................................................................................................................. I I 第一章绪论............................................................................................................... III 1.1引言.. (1)
1.2 钯催化烯丙基羧酸酯烯丙位的偶联反应 (1)
laraine1.2.1碳碳键的偶联 (2)
1.2.2碳硅键的偶联 (14)
1.2.3碳氮键的偶联 (16)
1.2.4碳氧键的偶联 (19)
1.2.5碳磷键的偶联 (22)
1.2.6碳硫键的偶联 (23)
1.2.7碳硼键的偶联 (26)pabx
1.3 钯催化烯丙基羧酸酯碳碳双键的偶联反应 (28)
1.3.1分子内烯烃迁移插入 (28)
1.3.2分子间烯烃迁移插入 (35)
1.4本课题的研究内容、目的及意义 (38)
1.4.1本课题的研究目的及意义 (38)
1.4.2本课题的研究内容 (38)
第二章钯催化烯丙基炔酸酯与异腈偶联反应的研究 (39)
2.1引言 (39)
2.2结果与讨论 (40)
2.2.1化学药品与试剂 (40)
2.2.2典型实验操作 (42)
2.2.3反应条件优化 (43)
2.2.4底物拓展 (44)
现在完成时练习题2.2.5产物衍生化 (48)
2.2.6可能的反应机理 (49)
2.2.7产物表征 (50)
2.2.8化合物数据 (51)
2.2.9化合物谱图 (60)
2.3本章小结 (88)
第三章钯催化烯丙基羧酸酯、降冰片烯及联硼酸酯偶联反应的研究 (89)代表英语
3.1引言 (89)
3.2结果与讨论 (90)
3.2.1化学药品与试剂 (90)
3.2.2典型实验操作 (92)
3.2.3反应条件优化 (92)
3.2.4底物拓展 (94)
3.2.5结构确定 (99)
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3.2.6控制性实验 (100)
3.2.7可能的反应机理 (101)
3.2.8产物表征 (102)
3.2.9化合物数据 (102)
新年好英文3.2.10化合物谱图 (113)
3.3本章小结 (134)职业培训
全文总结 (135)
参考文献 (136)
附录: 化合物一览表 (149)
攻读硕士学位期间取得的研究成果 (151)
致谢 (153)
