Organolithium with oxygen

Exposure of alkyllithium or aryllithium compounds to the atmosphere may cause degradation due to reaction with oxygen (equation 1) or air moisture (equation 2). Certain organolithium compounds are unstable at room temperature in the neat form, and require dilution even then they should best be stored at low temperature. The instability may be the result of reactions such as the eliminations depicted in equations 3 and 4, taking place as the temperature rises . 

Because they are so reactive, organolithiums are usually reacted at low temperature, often -78 °C (the sublimation temperature of solid CO2), in aprotic solvents such as Ht20 or THF. Organo-lithiums also react with oxygen, so they have to be handled under a dry, inert atmosphere of nitrogen or argon. 

Reductive 1,2-eIimination of chlorine and bromine from adducts of l-bromo-2-chlorocyclo-propene (see Section 5.2.2.1.2.5.) with oxygen and sulfur hetarenes has served in the synthesis of a number of cycloproparenes. This transformation is effected by low-valent titanium together with lithium aluminum hydride or an organolithium compound. Thus, reaction of the adduct 3 of l-bromo-2-chlorocyclopropene and 1,3-diphenylisobenzofuran with tita-nium(III) chloride and lithium aluminum hydride overnight in tetrahydrofuran led to elimination of both halogens together with extrusion of the oxygen and formation of 2,7-diphenyl-l/f-cyclopropa[ ]naphthalene (4) in 72% yield. 

The reaction of organolithium compounds with oxygen can be controlled to give, at low temperatures, a hydroperoxide or at higher temperatures an alcohol or phenol [43]. 

Organolithium compounds all react rapidly with oxygen, being usually spontaneously flammable in air, with liquid water and with water vapor. However, lithium bromide and iodide form solid complexes of stoichiometry (RLi(LiX)j 6 with the alkyls, and theseTo lidsare stable in air ... 

The easiest way to make oxidizable silanes is by condensation of an organolithium with the inexpensive dimethyldimethoxysilane. If enolates have to be silylated, it may be preferable to use the more reactive chlorodimethylalkoxysilanes. Introduced by Dieter Enders, a-lithiated RAMP- and SAMP-hydrazones (e.g., 78) are enolate-like species having an impressive track record for stereocontrolled synthesis. The chiral auxiliary enables the stereoselective introduction of the silicon substituent. Having oxidatively cleaved the hydrazone to restore the original carbonyl function, the latter may be diastereoselective reduced to either an (/ )- or (5)-alcohoI. The ultimate silicon/oxygen displacement thus produces either a meso- or a dl-Aio (Scheme 1-55). ... 

J-Oxygen-functionalised sp3 organolithium compounds react with alkenyl-carbene complexes to generate the corresponding cyclic carbene complexes in a formal [3+3] process (see Sect. 2.8.1). In those cases where the organolithium derivative contains a double bond in an appropriate position, tricyclic ether derivatives are the only products isolated. These compounds derive from an intramolecular cyclopropanation of the corresponding cyclic carbene complex intermediate [89] (Scheme 83). 

Arylcopper intermediates can be generated from organolithium compounds, as in the preparation of cuprates.95 These compounds react with a second aryl halide to provide unsymmetrical biaryls in a reaction that is essentially a variant of the cuprate alkylation process discussed on p. 680. An alternative procedure involves generation of a mixed diarylcyanocuprate by sequential addition of two different aryllithium reagents to CuCN, which then undergo decomposition to biaryls on exposure to oxygen.96 The second addition must be carried out at very low temperature to prevent equilibration with the symmetrical diarylcyanocuprates. 

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