Epoxides, vinyl higher

One of the subunits of the natural product (-)-macrolactin A, a strong anti-viral agent, has been synthesized as shown in the following scheme, involving the hydrotelluration of a enyne (a), and the opening of an epoxide with a vinylic higher-order cyanocuprate (b). ... 

Less satisfactory results have been frequently encountered in the related asymmetric cycloaddition of a vinyl epoxide to an isocyanate as in Scheme 8E.30 [160]. The modest enantioselectivities of this process are indicative of the competitive intramolecular nucleophilic addition with enantioface exchange. When the oxazolidinone was generated from an achiral substrate, somewhat higher enantioselectiviites were obtained presumably due to superposition of the enantioselection obtained in the ionization step. 

Kinetic resolution of chiral aUylic alcohols.7 Partial (at least 60% conversion) asymmetric epoxidation can be used for kinetic resolution of chiral allylic alcohols, particularly of secondary allylic alcohols in which chirality resides at the carbinol carbon such as 1, drawn in accordance with the usual enantioface selection rule (Scheme I). (S)-l undergoes asymmetric epoxidation with L-diisopropyl tartrate (DIPT) 104 times faster than (R)-l. The optical purity of the recovered allylic alcohol after kinetic resolution carried to 60% conversion is often > 90%. In theory, any degree of enantiomeric purity is attainable by use of higher conversions. Secondary allylic alcohols generally conform to the reactivity pattern of 1 the (Z)-allylic alcohols are less satisfactory substrates, particularly those substituted at the /1-vinyl position by a bulky substituent. 

A one-sided attachment of a vinyl-functionalized salen monomer to an MCM-41 material was reported by Janssen (95). In the epoxidation of 1-phenylcyclohexene with PhIO in acetonitrile, the Mn-functionalized structure 7g gave an ee of 75%, which is the same as for the soluble Jacobsen complex and considerably higher than that obtained with 7f. Morever, the chemoselectivity, the olefin conversion, and the enantioselectivity remained unchanged over four consecutive cycles. 

With respect to the photoinitiator and cycloaliphatic epoxide, there are fewer than ten products on the market. The choice is higher for vinyl ether diluents. 

Vinyl esters are thermosetting resins that consist of a polymer backbone with an acrylate or methacrylate termination. The backbone component of vinyl ester resins can be derived from epoxide, polyester or urethane but those based on epoxide resins have most commercial significance. Bisphenol A epoxy formed vinyl esters were designed for chemical resistance and commonly formulated for viscosity for use in filament winding of chemical containers. Typically styrene is used as a reactive dilutent to modify viscosity. Phenolic novolac epoxies are used to produce vinyl esters with higher temperature capability and good solvent resistance, particularly in corrosive environments, and their FRP composites have demonstrated initial economy and better life cycle costs compared with metals. 

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