Transition Metal-Catalyzed and -Promoted Reactions via Carbene and Vinylidene Complexes Generated from Alkynes
Transition Metal-Catalyzed and -Promoted Reactions via Carbene and Vinylidene Complexes Generated from Alkynes
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DOI：
10.5012/bkcs.2007.28.12.2153
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发表时间：
2007
影响因子：
1.7
通讯作者：
K. Ohe
中科院分区：
文献类型：
--
作者：
K. Ohe
本文研究了过渡金属诱导下含羰基或亚氨基亲核官能团的炔原位生成卡宾配合物的反应。这些反应性类卡宾物种通过基于亚乙烯基络合物的电环化的6-endo-dig环化模式或π-炔络合物中的5-exo-dig环化模式以高原子效率产生，并且已被发现在催化卡宾转移反应中充当通用中间体。重点综述了吡喃亚基、呋喃基卡宾、吡咯基卡宾和乙烯基卡宾配合物的产生和制备，及其在酰基环丙基乙烯亚基的[3，3] σ转移重排、催化环丙烷化反应、叶立德的[2，3] σ转移重排或缩合反应、与杂芳族化合物的开环和取代反应以及低聚炔的催化异构化反应中的应用。
The transition metal-induced in situ generation of carbene complexes from alkynes having a carbonyl or imino group as a nucleophilic functionality has been investigated. These reactive carbenoid species are generated with high atom efficiency through a 6-endo-dig cyclization mode based on the electrocyclization of vinylidene complexes or a 5-exo-dig cyclization mode in π-alkyne complexes, and have been found to serve as versatile intermediates in catalytic carbene transfer reactions. Highlighted and reviewed in this account are the generation and preparation of pyranylidene, furylcarbene, pyrrolylcarbene, and vinylcarbene complexes and their application to [3,3]sigmatropic rearrangement of acylcyclopropylvinylidenes, catalytic cyclopropanation reactions, [2,3]sigmatropic rearrangement or condensation reactions via ylides, ring-opening and substitution reactions with heteroaromatic compounds, and catalytic isomerization of oligoynes.