兰州大学机构库 >化学化工学院
N-杂环卡宾在苯并唑类磷配体的合成及烯丙基烷基化反应中的应用研究
Alternative TitleApplication Study of N-heterocyclic Carbenes in the Synthesis of Benzazole-Phosphine Ligands and Allylic Alkylation Reaction
任伟
Thesis Advisor杨尚东
2019-10-10
Degree Grantor兰州大学
Place of Conferral兰州
Degree Name博士
Degree Discipline有机化学
KeywordN-杂环卡宾 苯并唑类磷配体 烯丙基C-H活化 β-氨基磷酸 亲核试剂
AbstractN-杂环卡宾作为一个电中性分子,中心碳原子拥有一对孤对电子,具有较强的亲核性等特点,在有机催化领域得到了广泛的应用与发展。另一方面,作为一类具有强σ-供电子能力的富电子配体,对空气及氧化剂具有较好的稳定性,与金属形成的络合物具有较好的催化性能,常取代磷配体而广泛用于金属催化的各类反应中。因此,进一步设计与合成新型结构的N-杂环卡宾并探索其在各类反应中的应用也显得尤为重要。基于这些,本论文主要围绕N-杂环卡宾参与催化的反应进行探讨与研究。
一、我们以N-杂环卡宾为催化剂,空气作为绿色氧化剂,一锅法合成了一系列含不同取代基或不同结构类型的苯并唑类磷配体的前体。该体系具有较好的底物适用性及官能团兼容性。此外,该类苯并唑类磷配体的前体可以通过简单的还原进而转化为相应的苯并唑类磷配体。二、我们发展了一种经由钯/N-杂环卡宾催化的α-氰基磷酸酯与烯丙基苯的烯丙基C-H键活化烷基化反应,成功获得了一系列含不同取代基或官能团的烯丙基烷基化的目标化合物。该方法除了具有较好的底物适用性及官能团兼容性外,也为四取代β-氨基磷酸及其衍生物的合成提供了一种新的方法。此外,也可以通过简单地操作进一步将生成的烯丙基烷基化的产物有效地转化为α-烯丙基化的腈类化合物。三、我们探索了一种以N-杂环卡宾(NHC)为配体,钯催化下炔烃与各类亲核性试剂的烯丙基C-H键活化烷基化反应,成功地得到了一系列含不同取代基或官能团的烯丙基烷基化的产物。该方法具有较好的官能团兼容性及原子经济性。此外,该方法不需要额外的氧化剂及酸添加剂。此外,通过一系列简单地操作,也可以将得到的烯丙基烷基化的产物有效地转化为具有多种官能团化的产物,也进一步说明了该方法具有较好的潜在应用价值。
Other AbstractN-Heterocyclic Carbenes (NHC) as typical structural features, all carbenes are neutral and possess a pair of lone pair electrons and strong nucleophilic properties. Because of its good catalytic performance, it has been widely applied and developed in the field of organic catalysis. On the other hand, as a new type of electron-rich ligand with strong σ-donor and comparatively weak π-acceptor properties which displays excellent stability for air and oxidant. N-Heterocyclic carbenes are often substituted for phosphine ligands and are widely used in transition-metal-catalyzed cross-coupling reactions dues to the complexes formed by N-heterocyclic carbenes with metals have good catalytic properties. Therefore, it is particularly important to further design and synthesize novel N-Heterocyclic Carbenes and explore their applications in other reactions. Based on these, the following sections will mainly focus on the study of catalytic reactions involved by N-heterocyclic Carbene.
1. An efficient strategy for the synthesis of benzazole-phoshpine ligand precursors via N-heterocyclic carbene catalyzed the aerobic oxidative cyclization reaction has been performed and displayed a broader functional group tolerance and high atom economy. The efficacy of this transformation has been further applicated in benzazole-phoshpine ligand systhesis. 2. Allylic C-H alkylation of allylbenzene with α-cyano-phosphate ester has been achieved via Pd (II)/N-Heterocyclic carbenes (NHC) under the mild reaction conditions and provides the corresponding linear allylation product in moderate to good yields. This reaction establishes a new method to construct ß-amino phosphonic acid derivatives with tertiary phosphonates. In addition, the α-monoallylation of nitriles have also easily obtained by the simple transformations from the alkylation products under mild conditions. 3. The Palladium-N-heterocyclic carbene (NHC)-catalyzed allylic alkylation of various pronucleophiles with alkynes has been accomplished under mild conditions. The protocol exhibits broad functional group compatibility and high atom economy. Moreover, the catalytic process avoids the use of external oxidants and acid as additives. Furthermore, the successfully transformations of the functionalized allylation products to various versatile skeletons were achieved, which demonstrated the potential application utility of this synthetic protocol.
Pages161
URL查看原文
Language中文
Document Type学位论文
Identifierhttp://ir.lzu.edu.cn/handle/262010/340613
Collection化学化工学院
Affiliation化学化工学院
First Author AffilicationCollege of Chemistry and Chemical Engineering
Recommended Citation
GB/T 7714
任伟. N-杂环卡宾在苯并唑类磷配体的合成及烯丙基烷基化反应中的应用研究[D]. 兰州. 兰州大学,2019.
Files in This Item:
There are no files associated with this item.
Related Services
Recommend this item
Bookmark
Usage statistics
Export to Endnote
Altmetrics Score
Google Scholar
Similar articles in Google Scholar
[任伟]'s Articles
Baidu academic
Similar articles in Baidu academic
[任伟]'s Articles
Bing Scholar
Similar articles in Bing Scholar
[任伟]'s Articles
Terms of Use
No data!
Social Bookmark/Share
No comment.
Items in the repository are protected by copyright, with all rights reserved, unless otherwise indicated.