用于 Z-选择性烯烃复分解的改良钌催化剂。
Improved ruthenium catalysts for Z-selective olefin metathesis.
机构信息
Arnold and Mabel Beckman Laboratories of Chemical Synthesis, Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California 91125, USA.
出版信息
J Am Chem Soc. 2012 Jan 11;134(1):693-9. doi: 10.1021/ja210225e. Epub 2011 Dec 9.
Abstract
Several new C-H-activated ruthenium catalysts for Z-selective olefin metathesis have been synthesized. Both the carboxylate ligand and the aryl group of the N-heterocyclic carbene have been altered and the resulting catalysts evaluated using a range of metathesis reactions. Substitution of bidentate with monodentate X-type ligands led to a severe attenuation of metathesis activity and selectivity, while minor differences were observed between bidentate ligands within the same family (e.g., carboxylates). The use of nitrato-type ligands in place of carboxylates afforded a significant improvement in metathesis activity and selectivity. With these catalysts, turnover numbers approaching 1000 were possible for a variety of cross-metathesis reactions, including the synthesis of industrially relevant products.
摘要
已经合成了几种用于 Z-选择性烯烃复分解的新型 C-H 活化钌催化剂。改变了 N-杂环卡宾的羧酸盐配体和芳基，并用一系列复分解反应对所得催化剂进行了评估。用单齿 X 型配体代替双齿配体导致复分解活性和选择性严重衰减，而同一配体家族（例如羧酸盐）中的双齿配体之间观察到较小的差异。使用硝酮型配体代替羧酸盐可显著提高复分解活性和选择性。使用这些催化剂，各种交叉复分解反应（包括工业相关产品的合成）的周转数接近 1000。
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