Butyl phenylthio cuprate

(a) Katritzky, A. R. Handbook of Heterocyclic Chemistry, Pergamon Oxford, 1985 p 261. (b) Katritzky, A. R. Handbook of Heterocyclic Chemistry, Pergamon Oxford, 1985 p 245. 

Mark A. Collins Steven P. Tanis The Upjohn Company, Kalamazoo, MI, USA 

Analysis of Reagent Purity an assay to determine relative thermal stabilities can be used to estimate reagent quality and concentration a sample of known volume and temperature is quenched with excess PhCOCl, and the yield of PhCO(/ -Bu) 

Preparative Methods 1.0 equiv of butyllithium is added drop-wise toa0.2M,0°C THF solution of thiophenol in a three-neck flask equipped with N2 inlet, solid addition funnel, and rubber septum after stirring for 10 min, 1.0 equiv of copper(I) iodide is added via the addition funnel stirring for an additional 15 min provides a clear, yellow solution which is cooled to — 78 °C 1.0 equiv of w-BuLi is then added dropwise via syringe after 1 h, the light brown, opaque solution is ready for use. Alternate sources of PhSCu may be acceptable PhSCu in purities of 95- 98% is commercially available.  

Handling, Storage, and Precautions use in a fume hood best results are obtained with high-purity copper (I) salts, dry, O2-free solvents, and alkyllithium solutions free of contaminating alkoxides or hydroxides n-BuLi is pyrophoric, and due care must be exercised in its handling the reagent has greater stability in THF than in ether thermal decomposition is minimal at or below —25 °C but is substantial at 0 °C.  

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Lithium n butyl (phenylthio) cuprate has been used in nucleophilic substitution reactions of arenesulfonyl fluorides, al-lylic acetates, 9 BBN, propargyllc carbamates, and bromo-alkenes, as well as in nucleophilic additions to acetoxy-epoxides. It Is a good choice for 1,4-addItIon of an n-Bu group, having been used in 1,4 addition-elimination reactions of a-oxoketene dithloacetals and 3-halo-2-cycloalkenones, and in tandem vicinal dialkylation reactions of 5-methyleneoxa-zolones and alkynes. A typical example Is the use of the reagentin the stereospecific synthesis of (, -2-heptenoicacidfrom acetylene (eq 1). ... 

SECONDARY AND TERTIARY ALKYL KETONES FROM CARBOXYLIC ACID CHLORIDES AND LITHIUM PHENYLTHIO(ALKYL)CUPRATE REAGENTS tert-BUTYL PHENYL KETONE... 

Lithium, methyl, 55,7, 10 Lithium, phenyl-, 55,11 Lithium phenylthio(alkyl)cuprates, 55,122 LITHIUM, phenyltluo(fe/f-butyl)cuprate [Lithium, phenylthio( 1,1 -dimethyl-ethyl)cupiate, 55,122 Lithium, 1-propenyl-, 55, 111 LITHIUM, ( >l-propenyl-, 55, 103 Lithium thiophenoxide [Ben7enethiol, lithium salt], 55, 122... 

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