Epoxides reactions with organometallic compounds

Reactions of the epoxide of 1-butene with CH3Li gives a 90% yield of 3-pentanol. In contrast, reaction with CH3MgBr under similar conditions gives an array of products, as indicated below. What is the basis for the difference in reactivity of these two organometallic compounds toward this epoxide ... 

The nucleophilic carbon of an organometallic compound reacts with an electrophile. For example, in the following reactions, the organolithium reagent and the Grignard reagent each react with an epoxide. 

In Sect. 5.2.2, Example 5.12, we saw the electrophilic character of epoxide toward the alkoxide ion. The carbanion is another charged nucleophile that opens a three-membered ring in reaction with epoxides. When such an anion is unstabilized, its synthetic equivalent is an organometallic compound affording a-alkylated or arylated alcohols as products (Scheme 5.50a). 

Finally, a mention should be made about the one peroxo system which will become more and more dominant the organometallic oxides of rhenium(VII). Such compounds have been found to be of outstanding catalytic activity for a number of oxygen transfer reactions with hydrogen peroxide.92 The best studied complex is methyltrioxorhenium(VII) (MTO) and its congeners. Figure 2.32 illustrates its synthesis. Epoxidation, aromatic oxidation and halide oxidation with these complexes have been studied with hydrogen peroxide and shown to be remarkably efficacious. 

Precursor of Useful Chiral Ligands. OPEN is widely used for the preparation of chiral ligands. Organometallic compounds with these ligands act as useful reagents or catalysts in asymmetric induction reactions such as dihydroxylation of olefins, transfer hydrogenation of ketones and imines, Diels-Alder and aldol reactions, desymmetrization of meso-diols to produce chiral oxazolidinones, epoxidation of simple olefins, benzylic hydroxylation, and borohydride reduction of ketones, imines, and a,p-unsaturated carboxylates. ... 

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