Organolithium compounds reactions

Organolithium compounds. Reaction of the chlorohydrin (2) with n-butyllithium at — 78° and then lithium naphthalenide (1) results in the organolithium compound a,... 

Bachki A, Foubelo F, Yus M (1996) Chiral Epoxides as a Source of Chiral (3-Oxido-Functionalized Organolithium Compounds Reaction with Electrophiles. Tetrahedron Asymm 7 2997... 

We saw in Chapter 17 that organolithium compounds reaction with Cu(I) to give Gilman reagents. Thus organolithium compounds are important synthetic intermediates. 

It is sometimes necessary e.g., in reactions involving organolithium compounds or in certain Grignard preparations) to carry out a reaction... 

Another example illustrating the greater reactivity of organolithium compounds is the preparation of the otherwise difficultly accessible esters of 2-pyridyl-acetlc acid by the following series of reactions from a-picoline ... 

Many organic halides do not react satisfactorily with lithium to form RLi ecMnpounds or with metallic magnesium to form Grignard reagents. The desired organolithium compound can often be prepared by a halogen-metal interconversion reaction ... 

The reactions of organolithium compounds with carbonyl compounds, including carbon dioxide, may be interpreted as follows ... 

The most general synthetic route to ketones uses the reaction of carboxylic acids (or their derivatives) or nitriles with organometallic compounds (M.J. Jorgenson, 1970). Lithium car-boxylates react with organolithium compounds to give stable gem-diolates, which are decom-... 

Before we describe the applications of organometallic reagents to organic synthesis let us examine their preparation Organolithium compounds and other Group I organometal he compounds are prepared by the reaction of an alkyl halide with the appropriate metal... 

Organozmc reagents are not nearly as reactive toward aldehydes and ketones as Grig nard reagents and organolithium compounds but are intermediates m certain reactions of alkyl halides... 

PALLADIUM-CATALYZED REACTION OF ORGANOLITHIUM COMPOUNDS AND ALKENYL HALIDES ... 

Heptafluoro-2-naphthyllithiuni prepared by metalation reaction can thermally decompose to a hexafluoro-l,2-naphlhalyne by elimination of lithium fluoride [36, 37] In this organolithium compound, fluorine elimination can occur from either position 1 or 3, however, no evidence for fluorine elimination from position 3 IS observed... 

The reaction of tnfluoromethyl-substituted A -acyl umnes toward nucleophiles in many aspects parallels that of the parent polyfluoro ketones Heteronucleophiles and carbon nucleophiles, such as enarmnes [37, 38], enol ethers [38, 39, 40], hydrogen cyanide [34], tnmethylsilylcarbomlnle [2,47], alkynes [42], electron-nch heterocycles [43], 1,3-dicarbonyl compounds [44], organolithium compounds [45, 46, 47, 48], and Gngnard compounds [49,50], readily undergo hydroxyalkylation with hexafluoroace-tone and amidoalkylation with acyl imines denved from hexafluoroacetone... 

A more promising procedure for the formation of alkenes from tosylhydrazones is represented by the Shapiro reaction It differs from the Bamford-Stevens reaction by the use of an organolithium compound (e.g. methyl lithium) as a strongly basic reagent ... 

Although the effective functionality of CISi-PaMeSt was less than one, attempts were made to obtain block copolymers by coupling with living polyisoprenyllithium and a,w-disodium polyisobutylene glycolate. These particular coupling reactions were selected because it is known that Si-Cl bonds readily react with organolithium compounds and sodium alkoxides43 45 . 

Allenyl and 1- and 2-alkynyl sulfoxides have also been prepared by reaction of organomagnesium halides with sulfinate ester 19. 1-Alkynyl p-tolyl sulfoxides were prepared in good yield from 1-alkynylmagnesium halides plus ester 19 in toluene (equation ll)63. The corresponding organolithium compound was unsatisfactory as a... 

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