And organolithium reagents

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... 

Section 15 4 Grignard and organolithium reagents react with ethylene oxide to give primary alcohols... 

Suitable strong bases include the sodium salt of dimethyl sulfoxide (in dimethyl sulfoxide as the solvent) and organolithium reagents (in diethyl ether or tetrahydrofuran). 

Addition of Grignard and organolithium reagents to imines 2. derived from enantiomerically pure (S)-valinol (1), provides a-substituted phenethylamines 3 in moderate to good yield and excellent diastereoselectivity (in each case only one diastereomer can be detected by NMR)15. By appropriate selection of imine and organometallic reagent both diastereomeric amines are accessible (see also refs 16 and 17). 

Excellent results are achieved in the diastereoselectivc addition of Grignard and organolithium reagents to hydrazones 17 or 19 derived from either r,-ephedrine17 19 or L-valinol20. 

The Addition of Grignard Reagents and Organolithium Reagents to Aldehydes and Ketones... 

Decarboxylation reactions of metal carboxylates [Eq. (1)], are of increasing value in the synthesis of organometallic compounds (1-5). The reverse reaction, e.g., carbonation of Grignard and organolithium reagents (6,7), is a well-known source of carboxylic acids. Early reviews of the... 

Cross-coupling with Organomagnesium and Organolithium Reagents 315... 

As emphasized above, the practical utility of organocerium compounds is to circumvent the problems which are faced with the corresponding Grignard and organolithium reagents because of their inability to react effectively with sterically demanding carbonyl compounds and carbon-heteroatom unsaturated bonds which have acidic a-protons. Some of the latest examples are shown below. 

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