The acid-catalyzed reductive α-alkylation of β-aminothiophenes was applied to the N-(thien- 3-yl) acetamide and alkyl N-(thien-3-yl) carbamates. Without reduction, β-amino α- vinylthiophenes were obtained when α-branched aldehydes were used. β-(3-Aminothien-2- yl) α, β-unsaturated ketones, esters and nitriles were also prepared from the corresponding α-functionalized acetals. These amines are intermediates in the formation of thieno [3, 2-b] ...