Alkoxides organomagnesiums

Organolithium and organomagnesium reagents are highly reactive toward most carbonyl compounds. With aldehydes and ketones, the tetrahedral adduct is stable, and alcohols are isolated after protonation of the adduct, which is an alkoxide ion. 

Most successful approaches involving addition reactions in the presence of chiral additives utilize organolithium, organomagnesium and the recently introduced organotitanium reagents, which are known to coordinate with amines, ethers, metal amides and alkoxides. 

TABLE 4. Structurally characterized organomagnesium alkoxides and aryloxides, showing their methods of preparation... 

Organomagnesium alkoxides and aryloxides have been utilized in only a few applications. Methyhnagnesium f-butoxide 68 has been used in the chemical vapor deposition of MgO films onto silicon substrates . MgO films with good crystallinity were grown at 800 °C on Si(lll) surfaces, whereas polycrystalline films were formed at 400 °C. Intermediate temperatures produced multiple crystallite orientations. Similar results were obtained for deposition onto Si(lOO) surfaces over this range of temperatures. 

The mechanisms are complex, particularly in the organomagnesium (Grignard) reactions. Several reactive species are present, and the product metal alkoxide can complex with unreacted organometallic. Furthermore, trace transition metal impurities in the magnesium used to prepare Grignard reagents appear to facilitate electron transfer and may cause the reaction to proceed at least partly by a radical pathway. See (a) J. Laemmle, E. C. Ashby, and H. M. Neumann, J. Amer. Chem. Soc., 93, 5120 (1971) (b) E. C. Ashby, J. Laemmle, and H. M. Neumann, Accts. Chem. Res., 7,272 (1974). 

Detailed reviews on the structures of organomagnesium compounds and the constitution of their solutions have been published [D, 1, 2]. These references, especially the first two, also cover alkylmagnesium hydrides, amides, alkoxides and thiolates. However, while all of these compounds are of intrinsic interest, they are little used in synthesis. 

In addition to organohthium compounds, other reagents such as organomagnesium compounds and potassium alkoxides have also been used as initiator for anionic polymerization of masked disilenes. ... 

A striking exaple of the influence of the Schlenk equilibrium on the progress of reactions of organomagnesium compounds was observed in, what was named, a ligand-assisted nucleophilic addition reaction (LANA), in which the substrate was a lithium quinol alkoxide [29]. In a typical LANA reaction (Scheme 14) the lithium quinol alkoxide is first prepared in situ, after which follows the sequential addition of l,3-dimethyl-3,4,5,6-tetrahydro-2(l//)-pyrimidone (DPMU) and a Grignard reagent. 

---