本文選題：1 + 6-烯炔��； 參考：《浙江大學》2017年博士論文

【摘要】：五元碳環(huán)和五元雜環(huán)作為基本骨架存在于許多天然產(chǎn)物,藥物分子和功能材料中。如何高效構(gòu)建這些環(huán)狀化合物是合成化學家長期關(guān)注的問題。過渡金屬催化的1,6-烯炔氫官能團化環(huán)化反應(yīng)可以高效地構(gòu)建五元環(huán)狀化合物。目前催化劑的中心金屬主要為鈀,銠等貴金屬,同時反應(yīng)在底物范圍、區(qū)域選擇性調(diào)控以及不對稱催化方面仍存在一定的局限性。廉價過渡金屬具有儲量豐富,價格低廉,生物兼容性好的特點,并在金屬催化的烯烴或炔烴氫官能團化反應(yīng)中有了初步的應(yīng)用。亞胺吡啶類配體是一類具有氧化還原性質(zhì)的配體,其鐵或鈷的配合物呈現(xiàn)出良好的穩(wěn)定性和反應(yīng)催化活性。本文圍繞VA唑啉亞胺吡啶配體的高效合成和含亞胺吡啶類配體促進的鐵鈷催化1,6-烯炔氫官能團化環(huán)化反應(yīng)兩個方面展開,具體包括以下內(nèi)容:1)鈀催化手性VA唑啉2位C-H鍵的(雜)芳基化反應(yīng)合成手性VA唑啉配體以1,2-雙(二苯膦)乙烷(dppe)作為配體實現(xiàn)了鈀催化手性VA唑啉2位C-H鍵的(雜)芳基化反應(yīng),可高效地構(gòu)建VA唑啉亞胺吡啶配體(OIP)。同時利用我們發(fā)展的新策略可以構(gòu)建多種類型手性VA唑啉配體。2)鐵催化1,6-烯炔還原環(huán)化反應(yīng)以VA唑啉亞胺吡啶(OIP)作為配體,實現(xiàn)了鐵催化1,6-烯炔的還原環(huán)化反應(yīng)。該反應(yīng)具有很好的底物適用范圍和官能團容忍性,如羥基,酮羰基,酯基,醚,酰胺,亞胺,氰基,硅基和炔基等官能團。根據(jù)氘代實驗我們提出了可能的反應(yīng)機理。初步探究了鐵催化1,6-烯炔還原環(huán)化反應(yīng)的對映體選擇性。3)鈷催化1,6-烯炔硅氫化環(huán)化反應(yīng)合成并鑒定了亞胺吡啶鈷配合物(IP·CoCl2),利用該配合物實現(xiàn)了鈷催化1,6-烯炔的硅氫化環(huán)化反應(yīng),構(gòu)建了相應(yīng)的烷基硅化合物。該反應(yīng)具有很好的底物適用性,如酰胺,胺基,酯基,醚,氰基,鹵素,三氟甲基和雜環(huán)等官能團均能容忍。利用對比實驗和氘代實驗提出了可能的反應(yīng)機理。4)鈷催化區(qū)域選擇性可控的1,6-烯炔硼氫化環(huán)化反應(yīng)利用亞胺吡啶或VA唑啉亞胺吡啶為配體,實現(xiàn)了鈷催化區(qū)域選擇性可控的1,6-烯炔硼氫化環(huán)化反應(yīng),可以選擇性的構(gòu)建烯基硼化合物或烷基硼化合物。相應(yīng)的有機硼化合物可以經(jīng)過進一步的化學轉(zhuǎn)化成功構(gòu)建了取代的環(huán)狀化合物。利用對比實驗和氘代實驗,提出了可能的反應(yīng)機理。
[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.
【學位授予單位】：浙江大學
【學位級別】：博士
【學位授予年份】：2017
【分類號】：O621.251

【參考文獻】

相關(guān)期刊論文 前1條

1 靳立人,鄭劍峰,黃世俊,黃培強;手性二VA唑啉吡啶鐵和鎳配合物的制備與表征[J];無機化學學報;2003年11期

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本文編號：1798347