Sulfones reaction with organolithium

Recently, the reaction of organolithium compounds with magnesium carboxylates or sulfonates has been used to prepare organomagnesium compounds with increased selectivity towards carbonyl compounds (see Section 6.1) [32],... 

Cross-coupling reactions of aryl halides and sulfonates with organolithium and Grignard reagents, the Kharasch reaction... 

The simplest procedure for the sulfonation of polymeric organolithium compounds is the direct reaction with sultones. Thus, the functionalization of PSLi (Ain = 2.7 -4.7 X lO gmol" ) with generally a twofold molar excess of 1,3-propane sultone (eqn [23]) was investigated as a function of solvent and temperature. At temperatures from 3 to 80 ° C in benzene solution. 

The organolithium reagent (1) also reacts with a wide variety of other electrophiles, including silyl chlorides to provide bis(silyl)methane derivatives, and nitriles to provide -sUyl amines after in situ reduction of the intermediate imine derivative. a-Silyl epoxides are opened to provide the substituted vinylsilane. Reaction of (1) with arenesulfonyl fluorides provides a-silyl sulfones, key intermediates for the preparation of vinyl sulfones. Reaction of the lithium reagent (1) with alu-... 

Another dramatic example of the usefulness of DPE end-capping of polymeric organolithium compounds to promote efficient functionalization reactions is the sulfonation reaction using sultones [142]. A careful examination of the functionalization of poly(styryl)lithium with 1,3-propane sultone showed that the corresponding sulfonated polymer (see Eq. 32) was obtained in maximum yields of only 30% and 53% in benzene or tetrahydrofuran, respectively [142] ... 

The sulfonic acid moiety has been iacorporated iato a variety of nonfluofinated polymeric materials (111). Chain-end sulfonated polymers are produced by the reaction of sultones with polymeric organolithiums (112). Polymeric sulfonic acids such as these are iacorporated ia positive-working photoresist compositions (113). 

Whereas the reactions of sulfones with nucleophiles via pathways A and B of equation 1 are most frequently observed, the nucleophilic substitution reaction by pathway D has been observed only in the cases where the leaving carbanion can be stabilized, or in the highly strained molecules. Chou and Chang3 has found recently that an organolithium reagent attacks the sulfur atom of the strained four-membered sulfone in 34. When this sulfone is treated with 1 equivalent methyllithium, followed by workup with water or Mel, 38 or 39 are formed in high yield. 

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