新穎金屬催化有機反應運用在含氮與氧之雜環合成

Development of New Organic Transformation for Synthesis of N, O-Containing Heterocycles by Using Metal Complexes

帕加(vinayak vishnu pagar)

指導教授 ： 劉瑞雄

國立清華大學/理學院/化學系/博士(2014年)

https://doi.org/10.6843/NTHU.2014.00248

摘要

簡介
本文介紹利用過渡金屬催化合成新型態的有機轉化合成反應。我們使用金及銠金屬使進行各種溫合和具有立體選擇性以及轉換效率高的反應，並且廣泛應用於合成氮和含雜環的化合物合成。為了提供方便和更好的解釋，本論文共分為四個章節。

　　第一章介紹nitrosobenzenes和alkenylgold金屬亞甲基之間的兩個新又優質的環加成反應。本章研究結果我們獲得更好的產率來自nitrosobenzenes和alkenyldiazo酯類之間的金催化的[3+3]環加成反應得到喹啉氧化物。例如炔丙基酯，其所得金亞甲基與nitrosobenzene反應，得到alkenylimine，隨後[4 +2]環加成反應用於nitrosobenzene以形成1, 2-oxazines。

　　第二章討論oxa-Povarov反應/亞甲基產生一系列的alkenyldiazocarbonyl化合物的發展。一個三氟甲磺酸催化乙烯基重氮基反應與二苯氧基甲基苯，得到含有重氮環加成並且具有立體選擇性成效卓越的化合物探討。在許多天然物以及生物活性分子出現以dihydrobenzopyran為核心的分子。

　　第三章的部分，探討vinyldiazo羰基物種和縮醛之間的金催化反應，得到選擇性E-configured alkyl 3,5-dimethoxy-5-pent-2- enoates並且有良好的產率。根據我們的實驗數據，該反應順序包括一個初始Prins型反應，隨後金–亞甲基生成。這類型反應的成功指出的重氮官能基上相鄰的碳陽離子穩定化的效果。

　　第四章使用金催化oxa-Povarov反應，其中包括合適的diaryloxymethylarenes和芳基取代烯烴反應得到dihydrobenzopyrans產物；他們的[4+2]環加成反應是由高效率金催化得到高立體選擇性催化。其環加成反應在溫合條件下均適用於廣泛的化合物。產物的分析闡釋了該反應可能經過一個逐步的離子反應機構，因為這兩個E-和Z位向的β-甲基苯乙烯，得到相同的環加成產物和相同的比例。

關鍵字

金金屬催化反應 ； 氮氧雜環 ； 波瓦羅夫反應

並列摘要

Abstract
This dissertation describes development of new synthetic organic transformations by using transition metal catalysis. The use of gold and rhodium metals enables mild, diastereoselective and efficient transformations of variety of readily available substrates to wide range of synthetically useful nitrogen and oxygen containing heterocyclic products. For convenience and better understanding, this thesis is divided into four chapters.
The first chapter describes the two new formal cycloaddition reactions between nitrosobenzenes and alkenylgold carbenoids. We obtained quinoline oxides in good to better yields from the gold-catalyzed [3+3]-cycloadditions between nitrosobenzenes and alkenyldiazo esters. For propargyl esters, its resulting gold carbenes react with nitrosobenzene to give alkenylimine, followed by a [4+2]-cycloaddition with nitrosobenzene to form 1, 2-oxazines.

The second chapter deals with the development of an oxa-Povarov reaction/carbene generation sequence for alkenyldiazocarbonyl compounds. A triflic acid catalyzed reaction of vinyl diazoacetate with diphenoxymethylbenzene to give diazo-containing cycloadducts stereoselectively with fruitful range of substrate scope. The dihydrobenzopyran core moiety found in many natural product and bioactive molecules.

The third chapter explains, the gold-catalyzed reactions between vinyldiazo carbonyl species and acetals to obtain selectively E-configured alkyl 3,5-dimethoxy-5-pent-2- enoates in good yields. According to our experimental data, this reaction sequence involves an initial Prins-type reaction, followed by gold-carbene generation. The success of this Prins-type reaction indicates a stabilization effect of the diazo functionality on the adjacent carbocation.

The fourth chapter provides gold-catalyzed oxa-Povarov reactions involving readily available diaryloxymethylarenes and aryl-substituted alkenes to give dihydrobenzopyrans; their [4+2]-cycloadditions are efficiently catalyzed by gold catalysis with high diastereoselectivity. The cycloadditions were applicable to broad range of substrate under ambient conditions. Product analysis reveals that the reaction likely proceeds via a stepwise ionic mechanism because both E- and Z-configured β-methylstyrene gave the same cycloadducts in the same proportions.

並列關鍵字

Gold-catalysis ； N, O-Containing Heterocycles ； Povarov Reaction ； Oxa-Povarov Reaction

參考文獻

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