Chlorotriflamidation of vinylsilanes with N,N-dichlorotriflamide

Synthetic Approaches for the Construction of Five- and Six-Membered Silaazacycles

“…Shainyan and Ushakova demonstrated that chloromethyl(dimethyl)vinylsilane ( 48 ) reacted with N , N -dichlorotrifluoromethanesulfonamide to afford 1,3-azasilolidine 50 in 75% yield (Scheme 12 ). 22 The reaction is initiated by an oxidative haloamidation of the vinylsilane to give intermediate 49 via a free-radical mechanism. The high acidity of the proton on the triflimide moiety in 49 renders the intramolecular N-cyclization to give 50 via loss of HCl without the assistance of base.…”

Divergent reactivity of divinylsilanes toward sulfonamides in different oxidative systems

“…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. 11 Thus, the reaction in the system (t-BuOCl + NaI) 11a has been proven to be an effective approach to various heterocycles as shown in Scheme 1. Note, that the reactivity of triamide is principally different from that of arenesulfonamides.…”

Trifluoromethanesulfonamide vs. Non-Fluorinated Sulfonamides in Oxidative Sulfamidation of the C=C Bond: An In Silico Study

“…Amides are able to react with non-activated alkenes only under harsh conditions [ 7 ]; therefore, many attempts were made to discover amidation/aziridination techniques under mild conditions as well as to increase the yield of the target products. At present, there are several approaches for the activation of sulfonamide, in which the sulfonamido-containing precursors are represented by λ 3 -iodinanes (PhI=NTs) [ 8 , 9 , 10 , 11 , 12 , 13 , 14 ] and -brominanes [ 15 ], azides [ 16 , 17 , 18 ], chloramine-T [ 19 , 20 , 21 ], bromamine-T [ 22 , 23 ], N , N -dichlorosulfonamides [ 24 , 25 ], N -bromosuccinimide (NBS) and N -iodosuccinimide (NIS) [ 26 ], nitrido complexes [ 27 , 28 , 29 , 30 ] and combinations of sulfonamides with external oxidants [ 31 , 32 , 33 , 34 ].…”