Ring-closing metathesis in methanol and water

被引:136
作者
Kirkland, TA [1 ]
Lynn, DM [1 ]
Grubbs, RH [1 ]
机构
[1] CALTECH, Div Chem & Chem Engn, Arnold & Mabel Beckman Labs Chem Synth, Pasadena, CA 91125 USA
关键词
D O I
10.1021/jo981678o
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The ring-closing metathesis (RCM) of acyclic dienes in both methanol and water has been achieved through the use of water-soluble ruthenium alkylidenes. These alkylidenes react readily with acyclic olefins in protic solvents, but they do not cyclize alpha,omega-dienes because of the instability of the resulting methylidene. Successful cyclization has been achieved through simple substrate modification-incorporation of an olefin substituent allows cyclization to proceed in good yield. A methyl-substituted substrate was cyclized in 60% conversion in methanol, and the incorporation of a phenyl substituent resulted in nearly quantitative cyclization. Phenyl-substituted substrates are best suited for the reaction, as a more stable, active catalyst is regenerated upon each catalyst turnover. Using this methodology, 90% conversion of a water-soluble substrate to a substituted cyclopentene has been achieved in aqueous solution. This methodology has also been successfully applied to increase RCM yields in organic solvents.
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页码:9904 / 9909
页数:6
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