Assembly of Thiazino[3,4‐a]Isoquinoline and Thiazepino[5,4‐a]Isoquinoline Frameworks from Isoquinolinium 1,4‐Zwitterionic Thiolates Through [5+1] and [5+2] Cycloaddition Reactions

Abstract

Two cycloaddition modes of isoquinolinium 1,4‐zwitterionic thiolates have been established. Upon choosing α‐bromo ketones as the counterpart, a range of isoquinoline‐fused thiazines can be attained with yields ranging from moderate to excellent through a formal [5 + 1] reaction pathway, exhibiting remarkable substrate adaptability and resilience to diverse functional groups. Additionally, a library of unprecedented thiazepino[5,4‐a]isoquinolines, a novel category of seven‐membered heterocycles, has been synthesized via a [5 + 2] pathway utilizing acetylenedicarboxylate as the reactive component. Notably, this reaction process stands out for its exceptional 100% atomic utilization efficiency.