Synthesis and structure of organobismuth chlorides and triflates containing (C,E)-chelating ligands (E=O, S) and their catalytic application in the allylation of aldehydes with tetraallyltin

Four air-stable hypervalent organobismuth compounds with (C,O)- or (C,S)-chelating ligands, namely, R₂BiCl (R=2-(MeECH ₂)C₆H₄; E=O (3), S (4)), [2-(MeOCH ₂)C₆H₄]₂BiOTf (5), and [{2-(MeSCH₂)C₆H₄}₂Bi][OTf] (6; OTf=triflate) were successfully synthesized. The structures of compounds 3-6 were determined by single-crystal X-ray diffraction. Compound 6 comprises the [2-(MeSCH₂)C₆H₄]₂Bi⁺ cation and the OTf^- anion. Compounds 5 exhibited good catalytic efficiency and reusability for the allylation reaction of different aldehydes with tetraallyltin in methanol to give the corresponding homoallylic alcohols in excellent yields. Hyped up: Four air-stable hypervalent organobismuth compounds with (C,O)- or (C,S)-chelating ligands, R₂BiCl (R=2-(MeECH ₂)C₆H₄; E=O, S), [2-(MeOCH₂)C ₆H₄]₂BiOSO₂CF₃ (see picture) and [{2-(MeSCH₂)C₆H₄} ₂Bi][OSO₂CF₃], have successfully been synthesized and characterized. The pictured compound shows excellent catalytic activity and reusability for the allylation of aldehydes with tetraallyltin.