應用磷穩定雙原子碳作為配位基與鎳金屬進行醛和炔的還原偶聯催化反應;Using Phosphine-Stabilized-Dicarbon as a Ligand for Nickel-Catalyzed Reductive Coupling between Aldehydes and Alkynes

Please use this identifier to cite or link to this item: http://ir.lib.ncu.edu.tw/handle/987654321/84885

Title:	應用磷穩定雙原子碳作為配位基與鎳金屬進行醛和炔的還原偶聯催化反應;Using Phosphine-Stabilized-Dicarbon as a Ligand for Nickel-Catalyzed Reductive Coupling between Aldehydes and Alkynes
Authors:	賴雨岑;Lai, Yu-Tsen
Contributors:	化學學系
Keywords:	烯丙醇官能基;鎳金屬錯合物;還原偶聯催化反應
Date:	2020-10-20
Issue Date:	2021-03-18 16:44:37 (UTC+8)
Publisher:	國立中央大學
Abstract:	烯丙醇官能基為生物活性分子中常出現的有機分子片段，也能應用於許多合成方法學中。利用有機金屬催化醛和炔的還原偶聯反應來構建烯丙醇，至今已經有廣泛研究。但在現今的研究上尚未找到有效方法控制烯烴的區域選擇性和立體選擇性。在本篇研究中，我們利用本實驗室開發之雙原子碳 (phosphine-stabilized-dicarbon, PCC) 配位基鎳金屬錯合物，應用於醛和炔還原偶聯反應，並成功合成高選擇性之烯丙醇官能基衍生物。推測的機理是通過氧化環化形成五元鎳金屬環，接著進行還原脫去以提供三甲基矽烷基保護的烯丙醇產物。該反應結果顯示高區域選擇性及產率，與先前的文獻相比，有著巨大的演進。 ;Allylic alcohols are common and valuable organic moiety which can be applied in many synthetic methodologies for biologically active molecules. Therefore, constructing allylic alcohols by the reductive coupling of aldehydes and alkynes are essential topic to be studied. However, no effective method has been found to control the regioselectivity and stereoselectivity of olefins in these studies. Herein, we employed a new nickel catalyst supported by a newly designed dicarbon (phosphine-stabilized-dicarbon, PCC) ligand to mediate the reductive coupling reaction of aldehydes and alkynes, to generate highly selective allylic alcohol derivatives. The possible mechanism showed a ?ve-membered nickel metallacycle which formed by oxidative cyclization, followed the reductive elimination to provide the silyl-protected allylic alcohol products. This reaction proceeds with high regioselectivity which demonstrate a huge improvement compared to previous reports.
Appears in Collections:	[Graduate Institute of Chemistry] Electronic Thesis & Dissertation

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