AMIDO-DERIVATIVES OF METALS AND METALLOIDS .9. REACTIONS OF TIN(IV) AND TITANIUM(IV) AMIDES WITH COMPOUNDS HAVING CARBONYL AND SULPHINYL MULTIPLE BONDS

Titanium(IV) and tin(IV) amides (reactivity: Ti > Sn) are useful reagents for some organic aminations. Reactions of R3Sn·NMe2 (R = Me or Bun) or Ti(NMe2)4 with some carboxylic acids, anhydrides, amides, esters (alkyl, phenyl, enol, β-oxo, and αβ-unsaturated), an aldehyde, and acetone are reported. The following types were found: (i) (for most esters, CH2:CH·CO2H, and Ac2O), metathetical exchange with acyl-oxygen cleavage affording carboxylic acid amides; (ii) (for Me3Sn·NMe2 with CH2:CH·OAc), metathetical exchange with alkyl-oxygen fission; and (iii) (for Bun3Sn·NMe2 with AcOH), protonolysis. Amination of sulphur dioxide with Ti(NMe2)4 afforded SO (NMe2)2, while methyl sulphoxides (MeSOR: R = Me or C6H11) were reductively aminated by the same reagent to afford Me2N·CH2SR.