Organolithium reagent reactions

Organolithium reagents reaction with imidothioesters 114 reaction with isothiocyanates 42 reaction with non enethiolizable dithioesters 98 Orthotrithioesters 79 cleavage of 79 reaction with ketones 137 Oxathiane Eliel reagent 19 Oxaziridines as oxidising reagents 27 Oxiranes... 

Recently, a similar Michael-aldol tandem sequence has been reported, using catalytic amounts of the organolithium reagent. Reactions of a,f)-unsaturated esters with aldehydes were catalyzed by 0.2 equivalents of lithium phenylthiolate in the presence of phenyl... 

Tandem reactions involving organolithium reagents (reactions with formation and participation of heterocycles) 03OPP445. 

E. Organolithium Reagents Reaction with Other Functional Groups... 

E. Organolithium Reagents Reaction with Other Functional Groups The disconnection for ketone formation from the acid is ... 

These compounds are sources of the nucleophilic anion RC=C and their reaction with primary alkyl halides provides an effective synthesis of alkynes (Section 9 6) The nucleophilicity of acetylide anions is also evident m their reactions with aldehydes and ketones which are entirely analogous to those of Grignard and organolithium reagents... 

These reagents contain a negatively charged copper atom and are formed by the reaction of a copper(l) salt with two equivalents of an organolithium reagent... 

Reaction of organolithium reagents with aldehydes and ketones (Section... 

R Tl compounds, eg, methyl [3003-15-4], ethyl [687-82-1], isobutyl [3016-08-8], and phenyl [3003-04-1] thaHium(III), are usuaHy prepared by the reaction between a dialkyl or diarylthaHium haHde and an organolithium reagent in ether (16) ... 

All that has been said in this section applies with equal force to the use of organo-lithium reagents in the synthesis of alcohols. Grignard reagents are one source of nucleophilic carbon organolithium reagents are another. Both have substantial carbanionic char acter in their- car bon-metal bonds and undergo the same kind of reaction with aldehydes and ketones. 

Reaction of organolithium reagents with aldehydes and ketones (Section 14.7) Organolithium reagents react with aldehydes and ketones in a manner similar to that of Grignard reagents to form alcohols. 

Table 17.2 summarizes the reactions of aldehydes and ketones that you ve seen in earlier chapters. All are valuable tools to the synthetic chemist. Carbonyl groups provide access to hydrocarbons by Clemmensen or Wolff-Kishner reduction (Section 12.8), to alcohols by reduction (Section 15.2) or by reaction with Grignard or organolithium reagents (Sections 14.6 and 14.7). 

Reactions between organolithium reagents and 3-(2-naphthyl)-2H-azirine in the presence of a range of chiral ligands have been studied. The product aziridines are obtained in at best moderate ees [61]. 

The equatorial selectivity observed with organolithium reagents is enhanced in diethyl ether as the reaction solvent by the addition of lithium perchlorate (Table l)12. I3C-NMR studies47 indicate that the formation of a complex between lithium perchlorate and the carbonyl group, which also leads to a dramatic enhancement of the rate of the addition reaction, accounts for the increased diastereoselectivity. 

---