含亚胺吡啶类配体促进的铁钴催化1,6-烯炔氢官能团化环化反应研究

发布时间：2018-04-24 21:40

本文选题：1 + 6-烯炔　；参考：《浙江大学》2017年博士论文

【摘要】：五元碳环和五元杂环作为基本骨架存在于许多天然产物,药物分子和功能材料中。如何高效构建这些环状化合物是合成化学家长期关注的问题。过渡金属催化的1,6-烯炔氢官能团化环化反应可以高效地构建五元环状化合物。目前催化剂的中心金属主要为钯,铑等贵金属,同时反应在底物范围、区域选择性调控以及不对称催化方面仍存在一定的局限性。廉价过渡金属具有储量丰富,价格低廉,生物兼容性好的特点,并在金属催化的烯烃或炔烃氢官能团化反应中有了初步的应用。亚胺吡啶类配体是一类具有氧化还原性质的配体,其铁或钴的配合物呈现出良好的稳定性和反应催化活性。本文围绕VA唑啉亚胺吡啶配体的高效合成和含亚胺吡啶类配体促进的铁钴催化1,6-烯炔氢官能团化环化反应两个方面展开,具体包括以下内容:1)钯催化手性VA唑啉2位C-H键的(杂)芳基化反应合成手性VA唑啉配体以1,2-双(二苯膦)乙烷(dppe)作为配体实现了钯催化手性VA唑啉2位C-H键的(杂)芳基化反应,可高效地构建VA唑啉亚胺吡啶配体(OIP)。同时利用我们发展的新策略可以构建多种类型手性VA唑啉配体。2)铁催化1,6-烯炔还原环化反应以VA唑啉亚胺吡啶(OIP)作为配体,实现了铁催化1,6-烯炔的还原环化反应。该反应具有很好的底物适用范围和官能团容忍性,如羟基,酮羰基,酯基,醚,酰胺,亚胺,氰基,硅基和炔基等官能团。根据氘代实验我们提出了可能的反应机理。初步探究了铁催化1,6-烯炔还原环化反应的对映体选择性。3)钴催化1,6-烯炔硅氢化环化反应合成并鉴定了亚胺吡啶钴配合物(IP·CoCl2),利用该配合物实现了钴催化1,6-烯炔的硅氢化环化反应,构建了相应的烷基硅化合物。该反应具有很好的底物适用性,如酰胺,胺基,酯基,醚,氰基,卤素,三氟甲基和杂环等官能团均能容忍。利用对比实验和氘代实验提出了可能的反应机理。4)钴催化区域选择性可控的1,6-烯炔硼氢化环化反应利用亚胺吡啶或VA唑啉亚胺吡啶为配体,实现了钴催化区域选择性可控的1,6-烯炔硼氢化环化反应,可以选择性的构建烯基硼化合物或烷基硼化合物。相应的有机硼化合物可以经过进一步的化学转化成功构建了取代的环状化合物。利用对比实验和氘代实验,提出了可能的反应机理。
[Abstract]:Quaternary carbon rings and quaternary heterocycles are found as basic skeletons in many natural products, drug molecules and functional materials. How to efficiently construct these cyclic compounds is a long-term concern of synthetic chemists. The transition metal catalyzed cyclization of 1 ~ (6)-alkynyne can efficiently construct a quaternary cyclic compound. At present, the central metals of the catalyst are mainly palladium, rhodium and other precious metals. At the same time, there are still some limitations in the reaction range, region-selective regulation and asymmetric catalysis. Cheap transition metals have been widely used in metal-catalyzed hydrogenation reactions of alkenes and alkynes, because of their rich reserves, low price and good biocompatibility. Imine pyridine ligands are a kind of ligands with redox properties. Their iron or cobalt complexes exhibit good stability and catalytic activity. In this paper, the efficient synthesis of VAZolinimide pyridine ligands and the catalytic cyclization of 1zolinylenyl hydrofunctional groups catalyzed by iron-cobalt ligands with imidopyridine ligands were studied. The specific contents are as follows: Palladium catalyzed chiral VA azoline 2 C-H bond arylation synthesis of chiral VA azoline ligands using 1o 2 bis (diphenyl phosphine) ethane dppee) as ligand to realize palladium catalyzed chiral VA azoline 2 C-H bond Arylation reaction, VAZolinimide pyridine ligands can be efficiently constructed. At the same time, using the new strategy we developed, we can construct several kinds of chiral VA azoline ligands. 2) Iron catalyzed 1zolinimide pyridine (OIPP) as ligand to realize iron catalyzed reductive cyclization of 1zolinylenes. The reaction has good application range and functional group tolerance, such as hydroxyl group, ketone carbonyl group, ester group, ether, amide, imide, cyanide, silicon group and alkynyl group. According to the deuterium substitution experiment, we put forward the possible reaction mechanism. In this paper, the enantioselectivity of iron catalyzed reduction cyclization of 1zapyne was studied. 3) Cobalt catalyzed the cyclization of 1zene by hydrosilylation. The imine pyridine cobalt complex, IP CoCl2, was synthesized and characterized. The cyclization of 1h2ohlyne catalyzed by cobalt was carried out by using this complex. The corresponding alkyl silicon compounds were constructed. This reaction has good substrate applicability, such as amide, amine, ester, ether, cyanide, halogen, trifluoromethyl and heterocyclic functional groups can be tolerated. The possible reaction mechanism. 4) using imine pyridine or VA azolinimine pyridine as ligands was proposed by using comparative and deuterium experiments. The regioselectivity controlled cyclization reaction of 1-halidene borohydride catalyzed by cobalt was realized, and the alkyl boron compound or alkyl boron compound could be selectively constructed. The corresponding organic boron compounds can be successfully synthesized by further chemical conversion. The possible reaction mechanism was proposed by contrast experiment and deuterium experiment.
【学位授予单位】：浙江大学
【学位级别】：博士
【学位授予年份】：2017
【分类号】：O621.251

【参考文献】