以N_杂环卡宾为配体的金属络合物催化有机合成的反应_李林涛以N_杂环卡宾为配体的金属络合物催化有机合成的反应_李林涛.pdf

2001 年第 21 卷 有 机 化 学 Vol. 21, 2001 第 1 期, 75~ 81 Chinese Journal of Organic Chemistry No. 1, 75~ 81 #学术动态# 以 N-杂环卡宾为配体的金属络合物催化有机合成的反应 李林涛 麻生明X ( 中国科学院上海有机化 学研究所, 金属有机化学开放实验室 上海 200032) 摘要 综述了近几年来以 N- 杂环卡宾为配体的 金属络合物催化有机合成的反应。 关键词 N- 杂环, 卡宾, 金属络合物, 催化, 反应 Organic Transformations Catalyzed by N- Heterocyclic Carbene- Metal Complexes LI Lin-Tao, MA Sheng-Ming* ( Laboratory of Organometallic Chemistry , Shanghai Institute of Organic Chemistry , Chinese Academy of Sciences, 200032 Shanghai) Abstract Reactions catalyzed by N-heterocyclic carbene-metal complexes, such as olefin metathesis, coupling re- action, hydrosilylation reaction, etc. were reviewed. Ruthenium ( II) complexes bearing one or two imidazolin-2-ylidene ligands are highly active catalysts for all types of ring closing metathesis reactions. Importantly, they even allow the formation of tetrasubstituted alkenes that were not pre- viously achieved by ruthenium-phosphine metathesis catalysts. In addition, functionalized olefins were synthesized by in- termolecular cross-metathesis and ring-closing metathesis. Palladium( 0) complexes of imidazolin-2-ylidenes ( 19) could not catalyze the coupling of p-chlorotoluene and phe- nylboronic acid. However, a system consists of a Pd( 0) precursor and dihydroimidazoline carbene ligand, which is gen- erated in situ, showed high activity for Suzuki cross-coupling reaction of aryl chlorides with arylboronic acids, Kumada cross-coupling reaction of aryl chlorides with aryl Grignard reagents and amination of aryl chlorides. Complexes of the (NHC) Pd( PR3 ) I-2 type with bulky N-heterocyclic carbenes ( NHC) are efficient catalysts for the Suzuki and Stille cros