Self-Selection in Olefin Cross-Metathesis:  The Effect of Remote Functionality

Abstract

Olefin cross-metathesis (CM) is potentially an attractive method for generating dynamic combinatorial libraries (DCLs). In order for the CM reaction to be useful for DCL production, the course of the reaction and product distribution must be relatively insensitive to functionality remote from the reacting centers. We report on the CM of a series of allyl- and homoallylamides that are strongly dependent on remote functionality. This includes an unusual example of a cis-selective CM. [Reaction: see text]

Route to three-dimensional fragments using diversity-oriented synthesis

“…The subsequent RCM of 9a gave rise to two enamides, a major product 9b and a minor product 35b. In both products, migration of the double bond was observed, which is indicative of isomerization during the RCM reaction, presumably catalyzed by ruthenium hydride species (31,32). Formation of the sixmembered enamide 35b can be rationalized on grounds that the migration of the double bond occurred before the RCM releasing propene (instead of ethylene) to generate 35b.…”

Transition metals in organic synthesis: Highlights for the year 2005

“…Desymmetrizations of di-and trialkenyl phosphine oxides via CM were reported [1208]. An unusual cis-selective CM was reported [1209]. A non-carbenoid ruthenium complex catalyzed a CM of ethenylboronates with terminal alkenes to afford alkenylboronates (Eq.…”

Ring-Closing Metathesis Synthesis of Medium and Large Rings: Challenges and Implications for Sustainable Synthesis

“…The Grubbs-class ruthenium metathesis catalysts, while less sensitive to oxygen or water than the group 6 systems, are nevertheless susceptible to deactivation through chelation of (e.g.) carbonyl functionalities [76][77][78][79]. Instances of sensitivity to alcohol or amine functionalities have also been reported [80,81] (see also Section 4.1.2).…”