Diastereoselective Formation of Dithioacetal Oxides from Aliphatic Sulfines under Thermodynamic Control

Generation, Reactivity and Uses of Sulfines in Organic Synthesis

“…This does not compete with other methods in asymmetric synthesis. [131,132] Similar to this, Metzner et al [133] have described the diastereoselective formation of dithioacetal oxides from aliphatic sulfines by thiophilic attack. The sulfines were directly treated with organolithium compounds at -78°C in THF for 5 min, with thiophilic attack observed.…”

Mixed AggregAte (MAA): A Single Concept for All Dipolar Organometallic Aggregates. 2. Syntheses and Reactivities of Homo/HeteroMAAs

“…Bu( i -Bu) 3 AlLi, which has been used for the reduction of substituted cyclohexanones, was prepared by mixing solutions containing equimolar quantities of ( i -Bu) 3 Al and BuLi . The stereoselectivity of the reactions of α-lithio benzyl methyl sulfoxides with electrophiles depends upon the nature of the electrophile; it has been noted that their transmetalation with Et 3 Al occurs with inversion . Et 4 AlNa was synthesized from Et 3 Al and Na …”

The synthesis of thiols, selenols, sulfides, selenides, sulfoxides, selenoxides, sulfones and selenones

“…The addition of alkyllithiums to aliphatic sulfines generates lithiated α-sulfanyl carbanions which can be protonated with high diastereoselectivity (Scheme 86). 145 Interestingly, addition of triethylaluminium is thought to generate an aluminium 'ate' complex with inversion of configuration at the α-carbon. Subsequent quenching gives the opposite diastereoisomer with complete selectivity.…”

“…Subsequent quenching gives the opposite diastereoisomer with complete selectivity. 145 Aryl methyl sulfoxides have been resolved by formation of inclusion compounds with dehydrocholic acid. 146 In an interesting study, a variety of sulfoxides have been prepared essentially enantiomerically pure by kinetic resolution using an electrochemical-enzymatic system employing DMSOreductase.…”