The three-component reactions of o-iodobenzamides, elemental sulfur and dichloromethane (DCM) providing 2,3-dihydro-4H-benzo[e][1,3]thiazin-4-ones (2,3-dihydrobenzothiazinones) are accomplished via copper-catalyzed aryl CÀI thiolation and subsequent N-, S-hetero ring formation. In addition, the in situ aryl CÀI bond thiolation is also employed for the switchable synthesis of benzo[d]isothiazol-3(2H)ones (benzoisothiazolones) by subjecting o-iodobenzamides, elemental sulfur to the copper-catalyzed condition with microwave irradiation.

The tandem oxidation of the enaminone C=C double bond as well as subsequent C‐N bond formation are realized under metal‐free conditions by thermo‐induced free radical transformation. In the presence of benzoyl peroxide (BPO) and N‐iodosuccinimide (NIS), a series of tertiary α‐ketoamides are synthesized practically under aerobic atmosphere. The 18O isotopic experiment confirms that air is the source of oxygen in the newly generated carbonyl group.

The multicomponent reactions of iodobenzoic acids, aryl boronic acids, and dichloromethane (DCM) have been designed for the synthesis of various methylene‐bridged bis‐biaryl functionalized carboxylates. Under the catalysis of Pd(OAc)2, the formation of the products involves the cascade Suzuki coupling and CH2Cl2‐base bis‐esterification. The present work offers a direct and practical route to the synthesis of novel carboxylate scaffolds with extended diversity.