Ambident reactivity of enolizable 5-mercapto-1H-tetrazoles in trapping reactions with in situ-generated thiocarbonyl S-methanides derived from sterically crowded cycloaliphatic thioketones

• Grzegorz Mlostoń,
• Małgorzata Celeda,
• Marcin Palusiak,
• Heinz Heimgartner,
• Marta Denel-Bobrowska and
• Agnieszka B. Olejniczak

Beilstein J. Org. Chem. 2025, 21, 1508–1519, doi:10.3762/bjoc.21.113

• protonate this basic fragment, undergo 1,3-addition leading to corresponding products of S,S-, O,S-, or N,S-acetal type. For example, trapping of the in situ-generated adamantanethione S-methanide (1a) with tert-butylthiol or benzyl alcohol leads to the corresponding S,S-dithioacetal and O,S-thioacetal

Re₂O₇-catalyzed reaction of hemiacetals and aldehydes with O-, S-, and C-nucleophiles

• Wantanee Sittiwong,
• Michael W. Richardson,
• Charles E. Schiaffo,
• Thomas J. Fisher and
• Patrick H. Dussault

Beilstein J. Org. Chem. 2013, 9, 1526–1532, doi:10.3762/bjoc.9.174

• a Brønsted acid. Keywords: allylation; hemiacetal; O,O-acetal; O,S-thioacetal; peroxyacetal; Re2O7; S,S-acetal; Introduction The synthetically important conversions of hemiacetals to acetals, thioacetals, or homoallyl ethers are typically achieved through activation of the substrate with a strong