Phosphine vs DBU-Catalyzed Annulation Reactions of ß'-Acetoxy Allenoates with Acyl-Tethered Benzothiazole Bisnucleophiles: (4 + 3) or (4 + 1) vs (3 + 3) Annulation.

ABSTRACT

Dearomative annulation reaction of acyl-tethered benzothiazole bisnucleophiles with ß'-acetoxy allenoates by switching the Lewis base is developed. The DBU-catalyzed reaction gives benzothiazole-fused 1,4-dihydropyridine carboxylates by (3 + 3) annulation chemoselectively. By contrast, the PR3-catalyzed reaction gives benzothiazole-fused azepines by (4 + 3) annulation and cyclopentene carboxylates by (4 + 1) annulation; the ratio of the latter two products depends on the solvent. A possible rationale for the difference in the reactivity, based on the 1,4/1,5-addition of the 2-acyl-tethered benzothiazole to the key phosphonium intermediate, is provided.