期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 131, 期 30, 页码 10652-10661出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja904098h
关键词
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资金
- NIH [GM-59426]
- NSF [DBI-0619576]
Stereogenic-at-Mo monoalkoxide and monoaryloxide, complexes promote enyne ring-closing metathesis (RCM) reactions, affording the corresponding endo products with high selectivity (typically > 98: < 2 endo:exo). All catalysts can be prepared and used in situ. Five-, six-, and seven-membered rings are obtained through reactions with enyne substrates that bear all-carbon tethers as well as those that contain heteroatom substituents. The newly developed catalytic protocols complement the related exo-selective Ru-catalyzed processes. In cases where Ru-based complexes deliver exo and endo products nondiscriminately, such as when tetrasubstituted cyclic alkenes are generated, Mo-catalyzed reactions afford the endo product exclusively. The efficiency of synthesis of N- and O-containing endo diene heterocycles can be improved significantly through structural modification of Mo catalysts. The modularity of Mo-based monopyrrolides is thus exploited in the identification of the most effective catalyst variants. Through alteration of O-based monodentate ligands, catalysts have been identified that promote enyne RCM with improved efficiency. The structural attributes of three Mo complexes are elucidated through X-ray crystallography. The first examples of catalytic enantioselective enyne RCM reactions are reported (up to 98:2 enantiomer ratio and > 98% endo).
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