Acrylates Acyclic compounds

Oxoindolizines are obtained by reaction of ethyl pyrrolidinylideneacetate with several acyclic unsaturated carbonyl compounds by cyclization of the formed Michael adducts104 (equation 73). When this reaction was modified by changing the ring size of the enaminoester, the substitution pattern of the enone structure and by varying the conditions, different products were isolated105. N-acylation could be accomplished by reaction of acyl chlorides in the presence of pyridine. Bicyclic lactams are yielded by Michael addition of acrylic esters and NaH (equation 74). 

Trifunctional (meth)acrylate fluorine-containing cyclic and acyclic silane compounds have been prepared that form photocurable resin compositions. Coatings from these resins are anti-fouling and resist organic stains from oil mist and fingerprints without detracting from surface mar resistance. 

Cycloalkenyl sulfides 10 are converted into bicyclo[n.2.0] alkane compounds with almost complete enantioselectivity by the reaction with the fumaric or acrylic acid derivatives 2a,c as listed in Scheme 8 and Table 3. As the reactivity of 10 is not as high as that of acyclic alkenyl sulfides, the use of an equimolar amount of the chiral titanium reagent is required to attain a good chemical yield in some cases. Diastereoselectivity is generally excellent and no ene product is detected. 

Cross-metathesis of two different alkenes to give an acyclic alkene is complicated by the possible formation of not only the desired cross-metathesis product, but also self-metathesis products, each as a mixture of alkene isomers. However, some alkenes are amenable to efficient cross-metathesis to give the desired substituted alkene. This is particularly the case with alkenes that are slow to homod-imerize, such as a, -unsaturated carbonyl compounds or alkenes bearing bulky substituents. Hence, cross-metathesis of methyl acrylate with an alkene proceeds efficiently (2.116). The ruthenium catalyst reacts preferentially with the more electron-rich alkene 98, which then undergoes cross-metathesis with the acrylate or self-metathesis with another molecule of the alkene 98. The latter reaction is reversible and hence a high yield of the desired substituted acrylate results over time. The use of 1,1-disubstituted alkenes as partners in cross-metathesis provides a route to trisubstituted alkenes. This chemistry is therefore a useful alternative to conventional syntheses of alkenes, such as by the Wittig reaction. 

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