Iodine–DMSO-promoted divergent reactivities of arylacetylenes

Abstract

An unprecedented set of efficient, economical, atom-economic and exceedingly selective I2–DMSO-promoted methods is described for the generation of different structures.

γ-Aluminum Oxide-Mediated Iodination of Terminal Alkynes

“…106～107 ℃ (Lit. [10] 107～110 ℃); 1 Fluoro-4-(1,2,2-triiodovinyl)benzene (2b): [13] purified by silica gel column chromatography, eluting with petroleum ether afforded the title compound as pale yellow solid (969.7 mg, 97% yield). m.p.…”

“…m.p. 84～85 ℃; 1 H NMR (CDCl 3 , 400 MHz) δ: 7.27～7.24 (m, 2H), 7.07～7.03 (m, 2H); 13 Chloro-4-(1,2,2-triiodovinyl)benzene (2c): [13] purified by silica gel column chromatography, eluting with petroleum ether afforded the title compound as pale yellow solid (908. 6 Methyl-4-(1,2,2-triiodovinyl)benzene (2e): [11] purified by silica gel column chromatography, eluting with petroleum ether afforded the title compound as pale yellow solid (932.2 mg, yield 94%).…”

“…52～53 ℃ (Lit. [12] : 50～ 52 ℃); 1 Methyl-3-(1,2,2-triiodovinyl)benzene (2p): [13] purified by silica gel column chromatography, eluting with petroleum ether afforded the title compound as white solid (917.4 mg, 95% yield (3,4,4-Triiodobut-3-en-1-yl)benzene (2s): purified by silica gel column chromatography, eluting with petroleum ether afforded the title compound as pale brown oil (833.0 mg, 84% yield). 1…”

“…[8] On the other hand, efficient methods for the synthesis of 1,2,2-triiodovinyl derivatives are relatively rarely investigated in literatures. [9][10][11][12][13] Morisawa et al [10] revealed the preparation of 1,1,2-triiodo-1-propene derivatives in the presence of iodine and potassium hydroxide. Madabhushi et al [11] developed an oxyhalogenation reaction of alkynylsilanes with oxone-KI to obtain 1,2,2triiodovinyl derivatives in high yields.…”

“…Recently, Ahmed et al [13] described the synthesis of 1,2,2-triiodovinyl compounds from terminal alkynes in the presence of iodine and dimethyl sulfoxide (DMSO). However, some of these protocols developed so far would rely on the use of strong bases, hypervalent iodine compounds, or strong oxidizing agents, which may result in low functional-group tolerance and low yields.…”