From olefin cyclopropanation to olefin metathesis through catalyst engineering: recent applications of olefin metathesis to fine organic synthesis and to polymer chemistry
From olefin cyclopropanation to olefin metathesis through catalyst engineering: recent applications of olefin metathesis to fine organic synthesis and to polymer chemistry
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通过催化剂工程从烯烃环丙烷化到烯烃复分解：烯烃复分解在精细有机合成和高分子化学中的最新应用
DOI：
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发表时间：
1998
期刊：
影响因子：
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通讯作者：
A. Demonceau
中科院分区：
文献类型：
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作者：
A. Noels;A. Demonceau
概述了最近的合成突破所带来的新的发现，官能团宽容的后过渡金属（铑和钌）为基础的催化剂。尽管基于二铑（II）的络合物仅促进碳烯转移反应至烯烃（即烯烃环丙烷化），但可以设计和微调一些基于二铑的催化剂以介导碳烯转移反应或烯烃复分解。反应的不同结果可以通过金属中心配位或不配位卡宾和烯烃的能力来合理化。这种非常简单的方法表明，在金属中心的几个可用的配位位点有利于易位反应的烯烃环丙烷化的偏见。在开环易位聚合和共聚中的最近应用的实例包括聚二烯的后聚合物、碳水化合物取代的聚合物和遥爪低聚物的形成。通过冠醚类似物、不饱和肽和氨基酸、β-内酰胺和不同双环系统的形成来说明相同的基于铼的催化剂在闭环复分解中的应用。
An overview of the recent synthetic breakthroughs brought about by the discovery of new, functional group tolerant late transition metal (Rh and Ru)-based catalysts is proposed. Whereas dirhodium(II)-based complexes promote only carbene transfer reactions to olefins (i.e. olefin cyclopropanation), a few ruthenium-based catalysts can be engineered and fine tuned so as to mediate either carbene-transfer reactions or olefin metathesis. The different outcome of the reactions can be rationalized by the capability of the metal center to coordinate or not both the carbene and the olefin. This quite simple-minded approach indicates that several available coordination sites at the metal center favors metathesis reactions to the prejudice of olefin cyclopropanation. Examples of recent applications in ring opening metathesis polymerizations and copolymerizations include the formation of postpolymers of polydienes, of carbohydrate-substituted polymers and of telechelic oligomers. Application of the same ruthenium-based catalysts in ring-closing metathesis is illustrated by the formation of crown ether analogs, of unsaturated peptides and amino acids, of β-lactams, and of different bicyclic systems.