Bis phenylthio methyllithium

In the same paper the authors reported the preparation of a THF solution of bis(phenylthio)methyllithium. The lithio derivative is formed almost instantaneously and quantitatively (deuteration and NMR analysis). 

To a solution of bis(phenylthio)methane (2.324 g, 10 mmol) in THF (20 ml) stirred under nitrogen at 0°C, was added n-butyllithium (10 mmol) within 7 min to afford a clear yellow solution of the lithium compound, which can be used for reaction after 10 min and which is stable at 0°C for at least 12h. 

The two schemes showing homologation of halides through alkylation of phenylthiomethyllithium as the key step for carbon-carbon bond formation illustrate the potential of this reagent [303], 

Application to meihylidenatiun and epoxide formation will be described in Section 4.4.1. 

Methylthiomethyllithium was prepared by Peterson [304] from the reaction of dimethyl sulfide with the (TMEDA)-n-butyllithium complex. Subsequent reaction with benzaldehyde afforded the corresponding alcohol in an 84% yield. 

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For example, as shown in equation 43, Taguchi, Nozaki and coworkers reported in 1974 a one-carbon ring enlargement of cyclododecanone (187) to cyclotridecanone (190) with dibromomethyllithium through / -oxido carbenoid (188) . This reaction was expected to proceed via a one-carbon expanded enolate (189). Cohen and coworkers used the bis(phenylthio)methyllithium whereas Satoh and coworkers used a-sulfinyl lithium car-banion of 1-chloroalkyl aryl sulfoxides as the source of S-oxido carbenoids (equation 44) °. 

A further one-carbon atom insertion method is based on the rearrangement of the adducts of cyclic ketones with bis(phenylthio)methyllithium [43]. The... 

Recently, the following synthesis of secondary alcohols by the reaction of tri-alkylboranes with bis(phenylthio)methyllithium has been found (Eq. 22) . The... 

Yields of alcohols are appreciably lower when 2-lithio-l,3-dithiane is used in this sequence in place of bis(phenylthio)methyllithium. 

CuOTf-promoted elimination of thiophenol was exploited in two syntheses of 1-phenylthio-1,3-butadiene, one a C-C connective route from allyl bromide and bis(phenylthio)-methyllithium, and another from crotonaldehyde (eq 49). A topologically analogous C-C connective strategy provides 2-methoxy-1-phenylthio-1,3-butadiene from acrolein (eq 50). That the phenylthio rather than the methoxy substituent in 2-methoxy-1-phenylthio-1,3-butadiene controls the orientation of its Diels-Alder cycloadditions is noteworthy (eq 50). 

Cyclopropanation of enones.1 Reaction of an enone with tris(phenylthio)-methyllithium and then with CuOTf (1 equiv.) results in a bis(phenylthio)-cyclopropane (equation I). 

CONJUGATE ADDITIONS Bis(methylthio)(trimethylsilyl)methyllithium. Diethylalum-inum cyanide. Di(a-methoxyvinyl)copperlithium. Ethyl diethoxyacetate. Ethyl methylsulfinylacetate. Lithium a-carboethoxy vinyl(l-hexynyl)cuprate. Potassium fluoride. Quinine, chinchonine. Titanium tetrachloride. Trimethylaluminum. Tris-(phenylthio)methyllithium. 

The reaction of crotonaldehyde and methyl vinyl ketone with thiophenol in the presence of anhydrous hydrogen chloride effects conjugate addition of thiophenol as well as acetal formation. The resulting j3-phenylthio thioacetals are converted to 1-phenylthio-and 2-phenylthio-1,3-butadiene, respectively, upon reaction with 2 equivalents of copper(I) trifluoromethanesulfonate (Table I). The copper(I)-induced heterolysis of carbon-sulfur bonds has also been used to effect pinacol-type rearrangements of bis(phenyl-thio)methyl carbinols. Thus the addition of bis(phenyl-thio)methyllithium to ketones and aldehydes followed by copper(I)-induced rearrangement results in a one-carbon ring expansion or chain-insertion transformation which gives a-phenylthio ketones. Monothioketals of 1,4-diketones are cyclized to 2,5-disubstituted furans by the action of copper(I) trifluoromethanesulfonate. ... 

Methoxy(phenylthio)trimethylsilyl-methyllithium, 182 l-Methoxy-3-phenylthio-3-trimethyl-silyl-l-propenyl-3-lithium, 182 1 -Methoxy-4-(trimethylsilyl)-1 -butene-3-ynyl-2-lithium, 180 Methyllithium, 142, 188, 203, 214, 315 Methyllithium-Methylaluminum bis-(2,6-di-t-butyl-4-methylphenoxide), 203... 

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