Oxidatively assisted nucleophilic substitution of iodine in alkyl iodides by nucleofugic anions

Benzyne arylation of oxathiane glycosyl donors

“…Under these reaction conditions, nitrogen evolution and presumably benzyne formation, was much slower than when using lead tetraacetate as the oxidising agent. Further studies using the more reactive Zefirov’s reagent (µ-oxobis[(trifluoromethanesulfonato)(phenyl)iodine]) [36–37] were also undertaken. Preliminary results were promising yielding simple α-glycosides and a full study will be reported in due course.…”

From Solvolysis to Self-Assembly

“…Arguably, the most general and widely used methods114 of preparing alkynyliodonium species involves alkynylsilanes and in situ Zefirov’s reagent,115 48 , or the use of stannylalkynes,116 49 , and iodonium triflate, 50 ,117 as shown in Scheme 7. This later methodology affords a wide variety of β- functionalized alkynyliodonium salts, 51 .…”

Alkynes and Azides: Not Just for Click Reactions

“…The most downfield-shifted carbon reported was 133.16 ppm, but this still is unlikely for the C=N of the azirine. Further scrutiny of the literature was highly rewarding since 2-methoxy-2-phenylacetonitrile (16) is a known compound 17 and the characterization data matched that of the reported azirine (15). 2g The apparent misinterpretation of data was a minor point in a brief communication so we anticipated that this had gone unnoticed.…”

“…For our second generation attempt, we used an umpolung approach implementing hypervalent iodonium alkynyl triflates (HIATs) as electrophilic alkynes to be reacted with nucleophilic azide sources. 12 The use of HIATs stemmed from the work of Stang et al, 13 Zhdankin et al, 14 and Zefirov et al 15 in that they all clearly demonstrated the synthesis, isolation, and reactivity of these highly electrophilic, yet moderately stable species. In 1988, it was reported that when hypervalent iodonium phenylethynyl tosylate (12) was reacted with NaN 3 in MeOH at -70 °C and then warmed to ambient temperature, a 3% yield of an vinylidene carbene O-H insertion product (14) and a 23% yield of a substituted azirine (15) was observed (Scheme 5).…”

“…It is noted for safety that during recondensation an explosion of azidoacetylene is possible. Banert et al was able to characterize the azidoacetylene by 1 H, 13 C, 15 N, and IR at low temperatures. Additionally, they performed high-level calculations, working again with Auer et al, of the azido-acetylene and found that the calculated structure correlated closely with their spectroscopic information.…”