2,4,6‐Trichloro‐1,3,5‐Triazine: <scp> <i>N</i> , <i>N</i> </scp> ‐Dimethylformamide ( <scp>TCT: DMF</scp> ) Adduct as a Green Efficient Reagent for Synthetic Chemistry

ABSTRACT TCT: DMF adduct is a unique, versatile, and emerging solid green reagent prepared by the combination of 2,4,6‐trichloro‐1,3,5‐triazine and N , N ‐dimethylformamide. A key advantage of using TCT: DMF adduct as a catalyst is its ability to markedly shorten reaction time while achieving higher yields and selectivity. This review presents the first comprehensive literature highlighting the applications of TCT: DMF adduct as a catalyst under mild reaction conditions for various functional group transformations and heterocyclic syntheses. It is a Vilsmeier‐like iminium electrophilic complex efficiently works as chlorinating, dehydrating, and formylating agent. The electron‐deficient character of TCT: DMF adduct activates substrate in a short duration of time and substitution or nucleophilic attack of Cl − make it a valuable auxiliary for various synthetic reactions. It facilitates facile conversion of poor leaving groups like OH, and SO 3 H to their corresponding chlorides. The dehydrating property of this adduct enables the room temperature conversion of ketones to ketoximes and primary amines to nitriles. TCT: DMF actively participates in formylation and transesterification reactions. It has been established as best alternative of harsh and expensive reagents like SOCl 2 and POCl 3 /DMF. In heterocyclic synthesis, it serves as a key reagent for the synthesis of 2‐azetidinones, quinolones, 3,4‐dihydropyrimidinones/thiones, chromones, flavones, and isoflavones. Moreover, this review covers all catalytic activities of TCT: DMF adduct along with their reaction conditions and mechanisms that may be beneficial for various researchers.