Heterocyclization and solvent interception upon oxidative triflamidation of allyl ethers, amines and silanes

Triflamidation of Allyl-Containing Substances:Unusual Dehydrobromination vs. Intramolecular Heterocyclization

“…No products could be isolated from the NBS-induced reaction of allyl amine 10 with triflamide because of the strong polymerization of the reaction mixture. In contrast, allyl alcohol 11 afforded a low yield of amidine 12 , which was obtained earlier from the NBS-induced reaction of diallylformal with triflamide ( Scheme 8 ) [ 16 ].…”

“…Earlier, we studied a lot of unsaturated substrates in the reactions of oxidative sulfonamidation as summarized in review [ 12 ] but only a few of them contained electron-withdrawing groups. Among them were divinyl sulfone and divinyl sulfoxide, which reacted with triflamide in the system t -BuOCl/NaI via iodotriflamidation with subsequent cyclization into 2,6-diiodo-4-(triflyl)thiomorpholine 1,1-dioxide [ 13 ], mono- and diallyltriflamides, which under the same conditions reacted with carboxamides and sulfonamides via halogenation of the double bond [ 14 , 15 ] and/or iodosulfonamidation and cyclization to 3,7-diiodo-1,5-bis(triflyl)-1,5-diazocane and 3,7,9-tris(triflyl)-3,7,9- triazabicyclo[3.3.1]nonane [ 15 ], and mono- and diallyl ethers and allyl acetate, which on cooling to −30 °C gave the products of triflamidation or cyclization [ 16 ].…”

Visible‐Light‐Assisted Synthesis of Allylic Triflamides via Dual Acridinium/Co Catalysis

“…The marked Brønsted acidity of the “NHTf” motif (pKa ca. 6.3, for TfNH 2 ), [3a–c] the ready access to unprotected amino groups [3d–f] and the chemical flexibility of the allyl unit [2a,c] account for the prominent role played by this class of nitrogen‐based compounds in the organic chemistry scenario.…”

Divergent reactivity of divinylsilanes toward sulfonamides in different oxidative systems

“…Very recently, oxidative triamidation of several allylsilanes in different oxidative systems was shown to proceed with desilylation and formation of silicon-free products in the system (t-BuOCl + NaI), while no reaction occurred in the presence of Nbromosuccinimide (NBS). 9 Also noteworthy are the reactions of trimethyl(vinyl)silane and dimethyl(divinyl)silane in the absence of external oxidant but with pre-oxidized triamide in the form of N,N-dichlorotriamide leading to the products of achloro-b-triamidation in moderate yield. 10 Of particular relevance to the present work are two recent studies on the reactions of trimethyl(vinyl)silane 1 and dimethyl(divinyl)silane 2 with sulfonamides in different oxidative systems.…”