Grignard reagents sulfonates

Naphthoic acid has been prepared principally by the hydrolj sis of d-naphthonitriled the overall yields from (3-naph-thylamine, from sodinm-/3-naphthalene sulfonate, and from calcium d-naphthalene sulfonate being given as (approximately) 20 per cent, 21 per cent, and 50 per cent, respectively. The acid has been prepared also by the carbonation of the Grignard reagent from the less accessible /3-bromo derivative and. more recendy, from the readily available methyl ketone. ... 

Bromo-2-(t-butylsulfonyl)propene (79) reacts with nucleophiles such as lithium benzenethiolate, lithium enolates and Grignard reagents to give a, /(-unsaturated sulfones, which undergo nucleophilic addition of lithium cuprates (equation 68)58. 

Bromo-l-propenyl phenyl sulfone (104) can serve as a Michael acceptor to Grignard reagents to give cyclopropyl phenyl sulfones in good yields, (equation 85)70. Cyclopropanes prepared by this method are listed in Table 8. However, with methyl, ethyl or t-butyl... 

Grignard reagents, no detectable amount of cyclopropyl sulfones is formed. 

A procedure for a synthesis of dienyl sulfoxides (232 and 233) involves ring opening of dihydrothiophene 1,1-dioxide (231) by two molar equivalents of Grignard reagent (equation 141)136. The yields are usually in the 20-66% range. Similarly, treatment of the bicyclic sulfones 234, with 2 equivalents of phenylmagnesium bromide, produced a mixture of 1,4-dienylic sulfoxides (equation 142)136. 

The oxidative dimerization of the anion of methyl phenyl sulfone (from a Grignard reagent) in ethereal solution in the presence of cupric chloride in 5% yield has been reported47. Despite the reported48 poor stability of the a-sulfonyl C-centered radicals, Julia and coworkers49 provoked the dimerization (in 13 to 56% yields) of the lithiated carbanion of alkyl phenyl sulfones using cupric salts as oxidants. The best results are obtained with cupric triflates in THF-isobutyronitrile medium (56% yield for R = H). For allyl phenyl sulfones the coupling in the 3-3 mode is predominant. 

When a sulfonate ester possessing this type of chirality was converted to a sulfone with a Grignard reagent (10-129), inversion of configuration was found. This is not incompatible with an intermediate such as 147 but it is also in good accord with an Sn2 like mechanism with backside attack. 

If the rearrangement of oxime sulfonates is induced by organoaluminum reagents,the intermediate (71) is captured by the nucleophile originally attached to the Al. By this means an oxime can be converted to an imine, an imino thioether (R—N—C—SR), or an imino nitrile (R—N—C—In the last case, the nucleophile comes from added trimethyl si lyl cyanide. The imine-producing reaction can also be accomplished with a Grignard reagent in benzene or toluene. ... 

The formation of halogenation products from Grignard reagents and sulfonic acid anhydrides is the result of an oxidative reaction pathway . This side-reaction can be reduced by using sulfonic acid esters, however, in these cases alkylations as well as twofold sulfonylations (cf. corresponding results with sulfonyl fluorides ) are competing (equations 64 and 65). 

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