General Silver-Catalyzed Hydroazidation of Terminal Alkynes by Combining TMS-N₃ and H₂O: Synthesis of Vinyl Azides

Abstract

A general hydroazidation of unactivated alkynes using silver catalysis is reported. The reactions of diverse terminal alkynes with trimethylsilyl azide (TMS-N(3)) in the presence of H(2)O afforded the corresponding vinyl azides in good to excellent yields. This reaction has a broad substrate scope, good functional group tolerance, simple operation, and high reaction efficiency, thus providing an easy access to various functionalized vinyl azides.

DFT studies on the mechanism of Ag2CO3‐catalyzed hydroazidation of unactivated terminal alkynes with TMS‐N3: An insight into the silver(I) activation mode

“…Accordingly, the development of practical synthetic methods for the convenient preparation of newly functionalized vinyl azides is still highly appealing. Recently, Bi et al reported the first chemo‐ and regioselective hydroazidation of ethynyl carbinols to vinyl azides by Ag 2 CO 3 catalysis (Scheme ) . This represented a significant advancement for achieving regioselective hydrofunctionalization of alkynes.…”

Catalytic stereoselective addition to alkynes. Borylation or silylation promoted by magnesia-supported iron oxide and cis-diboronation or silaboration by supported platinum nanoparticles

“…[1] The interest in silver (I) catalysts stems from its possible coordination modes [2] and its affinity for hard donor atoms such as nitrogen or oxygen. [3] The instable, low-activity and easily decomposed AgI, [4] Ag2CO3, [5] AgSbF6 [6] and AgOTf salts [7] are used as Lewis acids and as sacrificial agents in some procedures for the preparations of gold (I) complexes. [8] In this context, it is important to establish whether or not stable Ag I complexes can exhibit good catalytic activity with respect to their silver salt precursors for certain reactions.…”

“…S21-S23 in the supporting information). It should be noted, however, that the reaction took place in only few minutes (6 min) at room temperature (26 ºC) for Ag (I) complexes 7, 10 and 11 (Table 1, entries 1, 2 and 3), compared to the slightly higher reaction temperature (50 ºC) and time (12 min) One important conclusion from Table 1 (entries [1][2][3][4][5][6] is that the cationic Ag I complexes were more active than the Cu I complexes and considerably more active than the Au I complex. This higher activity of Ag I and Cu I vs Au I can be explained by the lack of formation of di-cationic σ, π-disilver-(scheme 2: Top) or dicopper- [14] phenylacetylene adduct analogous to the fluxional…”

Silver‐Catalyzed Stereoselective Aminosulfonylation of Alkynes

“…In the last years,t he nitrogenation of alkynes with trimethylsilylazide (TMSN 3 )has attracted much attention, where carbon-carbon triple bond cleavage leads to av ariety of nitrogen-containing molecules. [8] Building from our recent efforts on the activation of alkynes by silver catalysis, [9] we herein report an ew strategy to effect radicalbased difunctionalization of terminal alkynes through an unprecedented hydroazidation/ radical addition cascade (Figure 1b). Thek ey point for this successful transformation is that we discovered amild and efficient approach to generate sulfonyl radical from sodium sulfinate,t hus avoiding the initial competitive radical addition to alkynes.…”