過渡金屬催化二烯炔類化合物的環化反應

Transition-Metal Catalyzed Cyclization of Dienyne

陳柏強(Po-Chiang Chen)

指導教授 ： 劉瑞雄

國立清華大學/理學院/化學系/碩士(2006年)

https://doi.org/10.6843/NTHU.2006.00196

摘要

摘 要

本論文主要是在針對二烯炔類化合物與金（Gold）催化劑反應的探討：首先會先就二烯炔類上官能基改變所造成的影響作探討；接下來將介紹利用串聯式（Tandem）的方法來改良反應。

首先觀察在二烯炔類化合物上置換不同的官能基（酯基、醇基、酮基、末端炔、非末端炔等等）的變化。

接著我們分別利用有機與金屬催化劑及金屬催化劑行串聯式（Tandem）的催化反應，使 3-en-1-yn-5-al 與環狀酮行醛-醇縮合反應（Aldol condensation），將反應的合成步驟大大的減少，而提高效率。

關鍵字

金 ； 催化劑 ； 二烯炔 ； 環化反應

並列摘要

This work investigates the feasibility of catalytic cyclization of 6,6-disubstituted 3,5-dien-1-ynes via a 1,7-hydrogen shift. On the basis of this structure-activity relationship, we conclude that such a [1,7]-hydrogen shift is characterized by a “protonic” hydrogen shift, which should be catalyzed by π-alkyne activators. We prepared various 6,6-disubstituted 3,5-dien-1-ynes bearing various functional group, and found their thermal cyclizations to be greatly enhanced by AuCl3.

To achieve the atom economy, we have developed a tandem aldol condensation-dehydration and aromatization catalysis between cycloalkanones and special 3-en-1-yn-5-als using the weakly acidic catalyst CpRu(PPh3)2Cl and connected organocatalyst & AuCl3.

The deuterium-labelling experiments reveal two operable pathways for metal-catalyzed [1,7]-hydrogen shift of 3,5-dien-1-ynes. Either concerted [1,7]-hydrogen shift or proceeds through a proton dissociation and reprotonation process.

參考文獻

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