Compound aryllithium

Organometallic compounds can be hydrolyzed by acid treatment. For active metals such as Mg, Li, and so on, water is sufficiently acidic. The most important example of this reaction is hydrolysis of Grignard reagents, but M may be many other metals or metalloids. Examples are SiRs, HgR, Na, and B(OH)2- Since aryl Grignard and aryllithium compounds are fairly easy to prepare, they are often used to prepare salts of weak acids, for example,... 

Molecular nitrogen (N2) reacts with aryllithium compounds in the presence of compounds of such transition metals as titanium, chromium, molybdenum, or vanadium (e.g., TiCl4) to give (after hydrolysis) primary aromatic amines. ... 

Alkyl and aryllithium compounds have been found to undergo 1,4-addition with the salts of a, (3-unsaturated acids.328 This result reflects the much reduced reactivity of the carboxylate carbonyl group as an electrophile. 

Aryllithium compounds have been investigated in quite some detail, including NMR and crystallographic studies of donor-containing compounds. An excellent overview of this chemistry has been provided in a 2004 review article.11... 

Similarly to the alkyl derivatives, the most common route for arylcopper compounds is the reaction of a copper halide and aryllithium compounds (Equation (4)). Organocuprates with aryl groups are obtained by using an appropriate excess of the lithium reagent. Magnesium aryls have also been employed in transmetallation reactions with Cu(l) salts to yield both arylcopper compounds and arylcuprates (Equations (5) and (6)). 

The action of chloroamine and bromoamine on organometallic reagents has been reviewed102 and a comprehensive review of electrophilic aminations of carbanions has appeared103. Alkyl, alkenyl and aryllithium compounds are converted into tertiary amines 84 by reaction with the mesityl compounds 83 (R2 = Me or Et Ar = 2,4, 6-MesCeHj)104. 

In contrast, tellurium insertion in alkyl- or aryllithium compounds followed by alkylation is a useful method for the synthesis of unsymmetrical tellurides. (For a tabulation of unsymmetrical tellurides prepared by alkylation of organyl tellurolates, see ref. 8.)... 

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 . 

An indirect oxidimetric titration method for alkylhthium compounds may be carried out, taking advantage of the fact that vanadium pentoxide causes fast and complete oxidation of alkyllithiums in solution. After the end of this reaction the reduced vanadium compounds are dissolved in sulfuric acid and titrated with Ce(IV) sulfate, using as indicator Ee(II) and 1,10-phenanthroline (64) sulfate. This method is inadequate for aryllithium compounds because the lithium phenoxide impurities reduce vanadium pentoxide. ... 

Similarly to compound 164, sterically crowded aryllithium compounds such as 167 crystallize with the lithium atoms 7i -coordinated to aromatic rings. Compound 167b crystallizes as a dimer, with the lithium atoms coordinated to one of the phenyl substituents... 

A function closely related to QCC is the Li quadrupolar splitting constant (QSC), defined as QSC = (1 -h/7 /3) x( Li), where r is the asymmetry parameter. The Li QSC values can be estimated from the Li and C(para) spin-lattice relaxation times. The QSC values are correlated with the effects of structure, solvent and temperature on association in solution for aryllithium compounds (155, 171, 172). Conclusions can be drawn about the structure of the associated species in cases where no supporting XRD evidence is available. ... 

The preparation of functionalized aryllithium compounds bearing an oxygen- or sulfur-containing functionality in a benzylic position is also possible by arene-catalyzed lithiation. When chlorinated materials 239 were deprotonated (for Y = OH, SH) with n-butyllithium in THF at —78 °C and then lithiated using DTBB as the catalyst at the same temperature. 

Various diboriodilithiomethanes of type 225 were synthesized by Bemdt and coworkers, adding different aryllithium compounds to the boron-carbon bonds of compounds 224a-e (Scheme 77) . The dilithium compounds have been characterized in the solid state by X-ray structural analysis. 225a-e adopt the structure of a 1,3-diborataallene system, where lithium-diethyl ether units are bridging the twisted B-C-B axis from both sides. 

A-Boc-indoline 166 is deprotonated by s-BuLi/TMEDA (Et20, —78 °C) preferentially in the 7-position to form the stannane 168 via the corresponding aryllithium compound" However, when the deprotonation is performed in the presence of (—)-sparteine in cumene, substitution in the 2-position is observed, to yield the stannane (S )-167 with e.r. = 99 1 (equation 38)". The change in regioselectivity is mainly caused by the bulky ligand 11, since with A,A -dibutylbispidine (169) the same regioselectivity (producing rac-167) is found. 

Arylium cations, 9 231, 241-243 Aryllithium compounds, crystal structures, 37 83-85... 

Selected NMR studies of aryllithium compounds with orf/io-NMe2 and -CH2NMe2 groups have also been described (35). 

Crystal Structures of Associated Alkyl-and Aryllithium Compounds and Complexes... 

Support-bound C,F I-acidic compounds, such as acetoacetamides, react with isocyanates under basic conditions to yield amides through C-carbamoylation [71]. Similarly, polystyrene-bound aryllithium compounds can be converted into benzamides by treatment with isocyanates [111]. These reactions are closely related to C-thiocarbamoyla-tion, which has been used for the solid-phase synthesis of thioamides (see Section 13.9). Amides have also been prepared by C-alkylation of resin-bound N-acylaminals with allyltrimethylsilane or diethylzinc (Entry 11, Table 13.7). 

The synthesis of benzo[6]thiophenes by the PPA-promoted cyclization of (arylthio)acetaldehyde dimethyl or diethyl acetals [Eq. (4)] was introduced by Tilak287, 288 in 1950 and improved in 1951.289 The acetals are readily prepared from aryl mercaptans and bromo-acetaldehyde dimethyl (or diethyl) acetal in the presence of sodium ethoxide, or by reaction of an aryllithium compound with [(MeO)2CHCH2S]2.290 Diethyl acetal as starting material sometimes gives better yields of product than the corresponding dimethyl acetal.291 Optimum yields of benzo[6]thiophenes are obtained when cyclization of the acetals is carried out under reduced pressure so that the lower boiling benzo[6]thiophenes distill as soon as they are formed. Experimental conditions for obtaining optimum yields vary from case... 

LiSiCl3 was probably formed by a halogen-metal exchange reaction, when an attempt was made to couple the highly hindered aryllithium compound 43 with BrSiCl3... 

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