Sulphinyl Carbanions

Important uses in synthesis have been demonstrated for carbanions 

Stereochemical studies concerning oc-sulphinyl carbanions have clarified the conflict of interpretation of recent years of kinetic preference in exchange of diastereotopic protons a to the sulphinyl group. Studies of cyclic sulphoxides have shown that small changes in dihedral angle 

Duhamel, P. Duhamel, and N. Mancelle, Bull. l c. chim. France, 1974, 331. 

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Formation of a-sulphinyl carbanions has been widely investigated378,379. Several bases have been found to be suitable for the generation of these carbanions, including the use of... 

In this section alkylation, Michael additions, hydroxyalkylation (reaction with carbonyl compounds), aminoalkylation, acylation and some other reactions of a-sulphinyl carbanions will be discussed. 

From the synthetic point of view the most important a-sulphinyl carbanions are the anions derived from dithioacetal S-oxides which may be considered as synthons of acyl... 

Durst and coworkers were the first to report the condensation of chiral a-sulphinyl carbanions with carbonyl compounds477. They found that metallation of ( + )-(S)-benzyl methyl sulphoxide 397 followed by quenching with acetone gives a mixture of dia-stereoisomeric /i-hydroxy sulphoxides 398 in a 15 1 ratio (equation 233). The synthesis of optically active oxiranes was based on this reaction (equation 234). In this context, it is interesting to point out that condensation of benzyl phenyl sulphoxide with benzaldehyde gave a mixture of four / -sulphinyl alcohols (40% overall yield), the ratio of which after immediate work-up was 41 19 8 32478. 

Cyclopropyl-2-hydroxyalkyl sulphoxides 416 can be obtained either by addition of an a-sulphinyl carbanion to a cyclopropyl ketone, or from alkyl 3-chloropropyl ketones and two moles of an a-sulphinyl carbanion493 (equation 247). 

Even with a-halocarboxylic acid esters 466 the attack of a-sulphinyl carbanion 467 takes place at the carbonyl carbon atom and not at the a-carbon atom and the corresponding a-halo-a-sulphinyl ketones 468 are obtained in high yields539-540 (equation 279). 

Solladie and coworkers545 confirmed the earlier result of Nishihata and Nishio546 that the carbonation of the a-sulphinyl carbanion proceeds under kinetic control with retention of configuration at the metallated carbon atom. However, they also found that the stereochemical outcome of this reaction depends on other factors. They observed that 90% of asymmetric induction may be achieved under kinetic control (reaction time < 0.5 min) by using a base with low content of lithium salts, a result consistent with an electrophilic assistance by the lithium cation (equation 286)545. 

Dialkyl cuprates may also be added to aryl vinyl sulphoxides and the resulting a-sulphinyl carbanions can be treated with various electrophiles such as aldehydes, ketones and alkyl halides (equation 350)643. 

In contrast to the early theoretical work of Rank and coworkers , C-NMR investigations had revealed that the metallated carbon atom in the a-sulphinyl carbanion is nearly planar . A four-centre chelate structure 315 has been proposed for a-lithiosulphoxides, and it is believed to be responsible for the planar configuration of the anionic carbon atom and for the greater stability of o(-sulphinyl carbanions in comparison with a-sulphenyl carbanions This chelation favours one of the two diastereoisomeric carbanions and for this reason a-sulphinyl carbanions react with electrophiles in a highly stereoselective manner (see below). 

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