Metal‐Free One‐Pot Conversion of Olefins and Alkynes to Amides Using TsNBr₂, I₂ and Aqueous NH₃ at Room Temperature

Abstract

A new synthetic procedure has been developed for the synthesis of primary aromatic amide from different types of styrene and phenylacetylene using TsNBr 2 , I 2 -aqueous NH 3 solution at room temperature. The reaction proceeds via the formation of α-bromoketone & α,α-dibromoketone as intermediate from styrene and phenylacetylene respectively in the presence of TsNBr 2 at the initial stage of the reaction. Subsequent treatement of the reaction mixturewith molecular iodine and aq. NH 3 (25%) produces the corresponding amide. Various primary aromatic amides were obtained in appriciable yield at room temperature.

Amide Bond Formation Strategies: Latest Advances on a Dateless Transformation

“…The transformation relies on the use of N,N-dibromo-p-toluene sulfonamide and iodine, to allow addition of OH-and substitution by NH3, respectively; it thus appears as suffering from poor atom economy and biocompatibility, although being working at room temperature. [55] Y: 57-80% I 2, NH…”

Unanticipated switch of reactivity of isonitrile via N≡C bond scission: Cascade formation of symmetrical sulfonyl guanidine

“…N,N -Dibromoarylsulfonamides are an important class of organic reagents used in various organic transformations. 48 , 49 , 50 , 51 , 52 , 53 , 54 , 55 , 56 , 57 , 58 , 59 , 60 In continuation of our effort in the development of synthetic methods with such reagents, herein, we disclose a new pathway for complete cleavage of C-N triple bond of isonitrile which leads to the formation of symmetrical guanidines. Interesting feature of this reaction is that in the initial phase, isonitrile works as a source of carbodiimide reacting via C-end of the isonitrile where no cleavage of C≡N bond occurs.…”