Transition Metal-Catalyzed Alkyne Activation Comprising Cycloisomerization, Hydrative Carbocyclizaton and Oxidative Cleavage Reaction

達斯(Arindam Das)

指導教授 ： 劉瑞雄

國立清華大學/理學院/化學系/博士(2009年)

https://doi.org/10.6843/NTHU.2009.00302

摘要

中文摘要

本論文分為五個章節，主要是利用過渡金屬催化環化異構化、水合環化以及分子內氧化斷裂反應的研究。
第一章主要是探討過渡金屬催化分子內三鍵環內六環環化反應反應中伴隨著結構的重組並生成的衍生物。我們發現反應是經由雙鍵的斷裂而造成亞烷基的轉移，而此類型的反應可很容易利用PtCl2、Zn(OTf)2，AuCl以及AuCl3催化進行反應。
第二章主要是探討利用三炔類化合物經由水合環化反應可得到雙螺環醇類化合物接著進行脫水反應可得到雙環酮類化合物。此反應是利用鉑催化經由選擇性的水合、三鍵的嵌入以及醛類化合物自身縮合反應。
第三章主要是探討一鍋化合成1，2-苯並菲的衍生物，反應利用PtCl2催化水合雙聚合反應生成二烷基一乙醯基苯。此反應經由三鍵選擇性的水合反應接著由雙酮基的中間體進行具有化學選擇性的雙聚化反應，而此類型的反應機構經由13C的標定實驗並分離出反應中間體進行驗證。
第四章主要是探討由氧化雙炔化合物利用過渡金屬PtCl2以及PPh3AuCl/AgOTf催化水合環化反應生成苯喃酮以及三螺環酮。而在反應中發現三鍵上鄰近的取代基會進而影響產物的位像選擇性。
第五章主要是探討利用過渡金屬金在室溫下利用氧氣使芳香基炔醚類進行氧化斷裂，此類反應可應用再C-H，C-C以及C≡C的斷裂。

關鍵字

金催化 ； 三鍵加成

並列摘要

ABSTRACT

Transition metal-catalyzed cycloisomerization, hydrative carbocyclization and oxidative- cleavage of appropriately functionalized organic molecules are described in this dissertation. For sake of convenience and better understanding, the thesis is divided into five chapters.
In the first chapter a new metal-catalyzed 6-endo-dig cyclization of 1-(2-(2-methylprop-1-enyl)phenyl)prop-2-yn-1-ol has been described, which produces substituted naphthalene derivatives with structural reorganization. In this process, we observed a 1,3-alkylidene migration via cleavage of the olefin double bond of the starting substrates. The ease and reliability of this cyclization were manifested by its compatibility with a wide diverse substrates and π-alkyne activators including PtCl2, Zn(OTf)2, AuCl and AuCl3.
The second chapter deals with a novel hydrative cyclization of triynes to afford bicyclic spiro alcohols, which undergo subsequent dehydration to give bicyclic ketones. This platinum catalysis has proposed to comprise a sequence of cascade reactions including, two selective hydrations, alkyne insertion and aldol condensations.
The third chapter describes, one-pot syntheses of chrysene derivatives via PtCl2-catalyzed hydrative dimerization of readily available 2-alkynyl-1-acetylbenzenes. This new tandem catalysis comprises an initial selective hydration of the alkyne, followed by chemoselective dimerization of diketone intermediates. The mechanism of this cyclization has been elucidated by 13C-labeling experiments as well as isolation of reaction intermediates.
The fourth chapter presents a unique synthesis of benzopyrones and tricyclic spiroketones from hydrative carbocyclization of oxodiyne substrates catalyzed by PtCl2 and PPh3AuCl/AgOTf, respectively. These distinct carbocyclizations with Pt and Au catalysts stem from their altered regioselectivity in the oxo-assisted hydration of the neighboring alkyne carbons.
The last chapter discusses a gold-catalyzed oxidative cleavage of aryl-substituted alkynyl ethers using molecular oxygen under ambient conditions; the transformation involves a remarkable cleavage of C-H, C-C and C≡C bonds simultaneous.

並列關鍵字

Transition Metal-Catalyzed Alkyne Activation

參考文獻

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Chapter II