Metathesis efficiency

For a review of asymmetric Mo-catalyzed metathesis, see Catalytic Asymmetric Olefin Metathesis, A. H. Hoveyda, R. R. ScHROCK, Chem. Eur. J. 2001, 7, 945-950 for reports on chiral Ru-based complexes, see (b) Enantioselective Ruthenium-Catalyzed Ring-Qosing Metathesis, T.J. Sei-DERS, D.W. Ward, R.H. Grubbs, Org. Lett. 2001, 3, 3225-3228 (c) A Recyclable Chiral Ru Catalyst for Enantioselective Olefin Metathesis. Efficient Catalytic Asymmetric Ring-Opening/Cross Metathesis In Air, J. J. Van Veldhuizen, S. B. 

Phosphine Dissociation Related to Initiation and Metathesis Efficiency... 

Grubbs Second-Generation Catalyst 277 Table 9.1 Initiation rates, phosphine exchange rates, and metathesis efficiency [13]. 

Scheme 9.1 Phosphine dissociation rates and metathesis efficiency (k.i/fcj)-...

The next critical step was to measure the alkene binding step. To investigate this, the partitioning of the 14-electron reactive intermediate between productive alkene metathesis (Step 2) reversion back to precatalyst (A .i) was probed. Unfortunately, the rate of alkene binding could not be directly determined instead, the metathesis efficiency ratio k /t2 was kinetically determined from a plot of 1//Toi,s versus [CygP]/[alkene]. 

In all cases, the aryhdenes showed metathesis efficiency quotients larger than that of 2 (Table 9.3) [18]. In each, the relative rate of return to the phosphine complex was faster than that for 2, which is consistent with the principle of microscopic reversibility. However, to make these catalysts truly superior to 2 would require increased stabilization of the Ru(IV) intermediate through alternative ligand modifications. 

Although unknown at the time, the reason for the latency of this complex was the fact that it rearranged to afford a cis-dichloro complex, where the neutral ligands also become cis to each other, a geometry that diminishes the metathesis efficiency [15]. 

Solid catalysts for the metathesis reaction are mainly transition metal oxides, carbonyls, or sulfides deposited on high surface area supports (oxides and phosphates). After activation, a wide variety of solid catalysts is effective, for the metathesis of alkenes. Table I (1, 34 38) gives a survey of the more efficient catalysts which have been reported to convert propene into ethene and linear butenes. The most active ones contain rhenium, molybdenum, or tungsten. An outstanding catalyst is rhenium oxide on alumina, which is active under very mild conditions, viz. room temperature and atmospheric pressure, yielding exclusively the primary metathesis products. 

Abstract For many years after its discovery, olefin metathesis was hardly used as a synthetic tool. This situation changed when well-defined and stable carbene complexes of molybdenum and ruthenium were discovered as efficient precatalysts in the early 1990s. In particular, the high activity and selectivity in ring-closure reactions stimulated further research in this area and led to numerous applications in organic synthesis. Today, olefin metathesis is one of the... 

Table 4 Comparative investigations efficiency of some metathesis catalysts...

Pyridine complexes of Pd- and Pt-pincer ligands are also suitable substrates for olefin metathesis [116]. The first-generation catalyst 9 efficiently mediates the RCM of diallylphosphines and diallyl sulfide when the heteroatom is com-plexed by a cationic [C5H5(NO)(PPh3)Re] moiety [117]. This principle has been exploited in the same study for tungsten, rhodium, and platinum complexes. 

An example of the efficient formation of an electron-deficient double bond by RCM was disclosed by a Japanese group in a novel total synthesis of the macrosphelides A (209) and B (208) (Scheme 41) [100]. When the PMB-pro-tected compound 204 was examined as a metathesis substrate, the ring closure did not proceed at all in dichloromethane using catalysts A or C. When the reaction was carried out using equimolar amounts of catalyst C in refluxing 1,2-dichloroethane, the cyclized product 205 was obtained in 65% yield after 5 days. On the other hand, the free allylic alcohol 206 reacted smoothly at room temperature leading to the desired macrocycle 207 in improved yield. 

A short and efficient synthetic approach to hydroxy-substituted ( )-stil-benoids, as exemplified by the natural compound resveratrol (371b) via solid-phase CM, was reported by a Korean group (Scheme 71) [154]. When two different stilbenes were allowed to couple by catalyst C, all three kinds of possible stilbenes were obtained as an inseparable mixture. Anchoring 4-vinylphenol to Merrifield resin, followed by exposing the supported styrenyl ether 368 and diacetoxy styrene 369 (10 equiv) to the catalyst, inhibited self-metathesis of the supported substrate. Sequential separation of the homodimer formed from 369 by washing and subsequent cleavage of the resin 370 with acid provided (E)-stilbene 371a with complete stereocontrol in 61% yield. 

Ongoing research efforts will lead to the arrival of even more efficient and selective metathesis catalysts with specifically tailored properties [196]. Due to the synergistic relationship between catalyst design and subsequent application in advanced synthesis [197], this progress will further expand the scope of metathesis and its popularity amongst the synthetic community. 

Until now, the most efficient approach to synthesize Freidinger lactams 147 started from a resin-bound cinnamylamine 144. A Fukuyama-Mitsunobu reaction to 145 followed by sulfonamide cleavage and a consecutive appropriate acylation built up the diene 146, which underwent ring-closing metathesis involving Grubb s catalyst 123 to generate the desired lactams 147 (Scheme 27, Table 5) [35d]. 

In 2002, Hoveyda et al. reported the synthesis, structure and reactivity of a chiral bidentate Ru-based catalyst 65, bearing a binaphthyl moiety, for olefin metathesis [33]. Preference for a bidentate chiral imidazolinylidene was based on the hypothesis that such a ligand would induce chirality more efficiently. This catalyst was designed by analogy with similar achiral complexes 66 that... 

The chemistry of lanthanide nitridoborates was developed by the more flexible and more efficient solid-state metathesis route by using nitridoborate salts and a lanthanide trichloride, at reaction temperatures as low as 600 °C. This type of reaction has been previously established and studied in some detail for reactions, such as the synthesis of lanthanide nitrides (LnN). Following this concept, lanthanum nitridoborates are obtained from reactions of lanthanum trichloride and lithium nitridoborate (or calcium nitridoborate), performed in a salt-balanced manner with respect to the formation of the co-produced liCl ... 

The choice of solvent may have a critical impact on efficiency too. In metathesis, dichloromethane, 1,2-dichloroethane and toluene are the solvents most commonly used. There are examples that show much higher yields in ring closing metathesis (RCM) when using fluorinated solvents [150]. An impressive effect of hexafluorobenzene as a solvent for CM is the modification of the steroid 93 the use of 1,2-dichloroethane leads to a very low yield and significant amounts of dimerisa-tion while the same reaction proceeds in 90% yield in C F (Scheme 3.14) [151]. 

During our efforts in profiling (comparative investigations) of several commercial available metathesis catalysts bearing NHC ligands in different types of metathesis reactions remarkable solvent effects were observed [4], Interestingly, the efficiency of most transformations studied frequently depended more on solvent and temperature effects rather than on the nature of Ru precursor and NHC ligands. 

The efficiency of the new catalysts 7a and 7b was examined in some metathesis transformations. Interestingly, both catalysts can only very slowly initiate typical metathesis reactions when tested at room temperature. At a catalyst loading of 5 mol%, chelating sulfur catalysts 7a and 7b achieved 22% and 51% conversion of diallylamide (3d), respectively, after heating to 80 C for 24 h. Catalyst 7a converts... 

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