Metathesis 3- methyl-1 -butene

It also explains the /Z selectivity of products at low conversions (kinetic ratio. Scheme 19). In the case of propene, a terminal olefin, E 2-butene is usually favoured (E/Z - 2.5 Scheme 19), while Z 3-heptene is transformed into 3-hexene and 4-octene with EjZ ratios of 0.75 and 0.6, respectively, which shows that in this case Z-olefins are favoured (Scheme 20). At full conversion, the thermodynamic equilibriums are reached to give the -olefins as the major isomers in both cases. For terminal olefins, the E olefin is the kinetic product because the favoured pathway involved intermediates in which the [ 1,2]-interactions are minimized, that is when both substituents (methyls) are least interacting. In the metathesis of Z-olefins, the metallacyclobutanes are trisubstituted, and Z-olefins are the kinetic products because they invoke reaction intermediates in which [1,2] and especially [1,3] interactions are minimized. 

A second observation was the fact that isomerization of the starting asymmetric olefin was much faster than the formation of new symmetric olefins. In fact, 40% of the initial cis olefin (Fig. 1) had isomerized to trans after only 4% conversion to new olefins. This result formally parallels the highly selective regenerative metathesis of a-olefins (60, 61), except that steric factors now prevail, because electronic effects should be minimal. Finally, the composition of the initially formed butene from r/j-4-methyl-2-pentene was essentially identical to that obtained when cA-2-pentene was used (18). When tra .v-4-methyl-2-pentene was metath-esized (Fig. 2), the composition of the initially formed butenes indicated a rather high trans specificity. 

The moderate specificity for forming m-2-butene initially (see Fig. 1) is again consistent with equatorial orientation of isopropyl the rather low cis specificity indicates only a moderate preference for equatorial orientation of the a-methyl, probably because of the offsetting weak repulsions caused by cis- 1,2-dimethyl-substitution. This effect is absent in the metathesis of tra i-4-methyl-2-pentene, and trans specificity for... 

The final stereochemistry of a metathesis reaction is controlled by the thermodynamics, as the reaction will continue as long as the catalyst is active and eventually equilibrium will be reached. For 1,2-substituted alkenes this means that there is a preference for the trans isomer the thermodynamic equilibrium at room temperature for cis and trans 2-butene leads to a ratio 1 3. For an RCM reaction in which small rings are made, clearly the result will be a cis product, but for cross metathesis, RCM for large rings, ROMP and ADMET both cis and trans double bonds can be made. The stereochemistry of the initially formed product is determined by the permanent ligands on the metal catalyst and the interactions between the substituents at the three carbon atoms in the metallacyclic intermediate. Cis reactants tend to produce more cis products and trans reactants tend to give relatively more trans products this is especially pronounced when one bulky substituent is present as in cis and trans 4-methyl-2-pentene [35], Since the transition states will resemble the metallacyclobutane intermediates we can use the interactions in the latter to explain these results. 

Scheme 7 Cross metathesis with symmetric olefins, (a) methyl oleate with m-2-butene-1,4-d iyl diacetate [67], and (b) 10-undecenoate with diethyl maleate [68]...

In the previous examples, disubstituted double bonds have been synthesized via ring-closing metathesis. As shown in Scheme 5, it is possible to extend the method to tri- or tetrasubstituted double bonds. Thus, bisallylic ether 33 leads to the trisubstituted olefin 34 and compound 35 gives the tetrasubstituted olefin 36 [3]. Here, the additional substituents are simple methyl groups, but silyl groups for example, can be introduced too. The volatile byproducts in these cases are not ethylene but butene or propene. 

Grabbs reported the use of (4a) in the synthesis of symmetrical trisubstituted olefins, wherein isomer selectivity is not an issue. Isolated yields using neat isobutylene or 2-methyl-2-butene as both reactant and solvent and a variety of functionalized metathesis partners were good to excellent under low catalyst loadings, providing a viable alternative to the Wittig reaction (equation 21). 

The photochemical reactions of arenecarboxylic acid esters with alkenes has received recent attention by Cantrell. - For example, irradiation of 2,3-dimethyl-2-butene and methyl benzoate gave a mixture of alkoxyoxetane (56), carbonyl-alkene metathesis product (57) and ketone (58), resulting from alkoxy radical allylic hydrogen abstraction and radical recombination. Such alkoxyoxetane photoproducts are... 

The reaction of a-olefins with (CO)5W[C(p-CgH4Me)2] supports the preferential formation of the ot,a -metallacycle (see Table 3). Only trace amounts of the olefins coming from the a,jS-substituted metallacycle are formed. Competition studies demonstrate that the relative reactivity of olefins toward metathesis is 1-pentene > 2-methylpropene > cis-2-butene > > 2-methyl-2-hexene. This stability pattern parallels the stability of 7c-olefin-metal complexes. 

In the presence of 1, the self-metathesis of allyl methyl sulfide (4), or its co-metathesis with 2-butene (6a) or 2-pentene (6b), actually occurs and leads to the expected products (Scheme 6) [40]. 

The only oxide that has been used for catalyzed olefin metathesis at 25°C is Re207/Al203 (in the middle of the 1960s by British Petroleum), but it suffered from a low number of active sites, side reactions caused by the acid support and deactivation of the catalyst. On die other hand, the silica-supported rhenium catalyst [(SiO)(Re(C-f-Bu)(=CH-f-Bu)(CH2-f-Bu)] catalyzes the metathesis of propene at 25°C with an initial rate of 0.25 mol/(mol Re x s). The formation of 3,3-dimethyl-butene and 4,4-dimethylpentene in a 3 1 ratio results from cross metathesis between propene and the neopentyl idene ligand, and die ratio of cross-metathesis products matches the relative stability of the metallacyclobutane intermediates. Cross metathesis of propene and isobutene and self-metathesis of methyl oleate can also... 

In addition, metathesis of 2-methyl-l-buten-4-yne occurs both at the double and the triple bond with the same catalyst. 

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