Reactions with Organometallic Reagents

Thallation in the 4-position of phenol was effected by its reaction in acetonitrile with [phenylthallium(lll)(18-crown-6)] diperchlorate under reduced pressure for 4 days at 60°C in the dark to afford in 97% yield [phenyl(4 -hydroxyphenyl-thallium(18-crown-6)]perchlorate (ref.64). 

By contrast, tri-n-butyltin methoxide reacted at the hydroxyl group rather than the ring to afford tri-n-butyltin phenoxide in 100% yieid by dropwise addition of the reagent under nitrogen to a refluxing solution of phenol in 1,2-dichloroethane and reaction over 2-3 hours (65). 

After conversion of phenol to O-phenyl diethylthiocarbamate, 2,2 -di(phenylthio)diphenyl disulphide has been obtained by the steps indicated (ref. 66). 

A reaction involving sulphur chemistry although more relevant to section 3.2.6 is the finding that phenols react with l-benzenesulphonylbenzotriazole in THF solution containing 1-methylimidazole at ambient temperature over 72 hours to give O-benzenesulphonyl deivatives in yields of 51-99% (ref.67). 

---

Pyran-4-one, 2,2-dimethyltetrahydro-reactions, with organometallic reagents, 3, 726 Pyran-4-one, 2,6-diphenyltetrahydro- C NMR, 3, 589... 

Nitriles are similar in some respects to carboxylic acids and are prepared either by SN2 reaction of an alkyl halide with cyanide ion or by dehydration of an amide. Nitriles undergo nucleophilic addition to the polar C=N bond in the same way that carbonyl compounds do. The most important reactions of nitriles are their hydrolysis to carboxylic acids, reduction to primary amines, and reaction with organometallic reagents to yield ketones. 

Intermolecular C-C Bond-forming Reactions with Organometallic Reagents... 

We begin, however, with a brief consideration of a group of phosphorus compounds of significance for their utility in the formation of carbon-phosphorus bonds via reaction with organometallic reagents in displacement reactions. 

Cross-coupling reactions with organometallic reagents... 

Coupling reactions with organometallic reagents 3.3.1 Kumada coupling... 

For additive effects on reactions with organometallic reagents, see a) H2O S. Ribe, P. Wipf, Chem. Commun. 2001,... 

---