Dihalo(imidazolium)sulfuranes: A Versatile Platform for the Synthesis of New Electrophilic Group-Transfer Reagents

Abstract

The syntheses of imidazolium thiocyanates and imidazolium thioalkynes from dihalo(imidazolium) sulfuranes are reported and their reactivities as CN(+) and R-CC(+) synthons evaluated, respectively. The easy and scalable preparation of these electrophilic reagents, their operationally simple handling, broad substrate scope, and functional group tolerance clearly illustrate the potential of these species to become a reference for the direct electrophilic cyanation and alkynylation of organic substrates.

Alkynylthioimidazolium Salts: Efficient Reagents for the Synthesis of Alkynyl Sulfides by Electrophilic Thioalkynylation

“…Anisotropic displacement parameter showna t5 0% probability level and hydrogen atoms omitted for clarity.Selectedb ond lengths []and angles[8]: C1ÀS1, 1.695(5);C3 ÀS1, 1.744(5); C1ÀC2,1.188 Anisotropic displacement parameter showna t5 0% probability level and hydrogen atoms omitted for clarity.Selectedb ond lengths []and angles[8]: C1ÀS1, 1.695(5);C3 ÀS1, 1.744(5); C1ÀC2,1.188…”

“…Following standard oxidation procedures, 17 could be selectively transformed either into sulfoxide 33 or sulphonylacetylene 34. [7] Selectedb ond lengths[ ]and angles [8]: C1ÀSe1, 1.839(4);C3 ÀSe1, 1.895(4);C1 ÀC2, 1.192(6);S e1ÀF1, 3.177( 4);C3 À Se1ÀC1, 96.38(18). [15] Thiophene 37 was also obtained from 17 after extensive heatingi nt he presence of Na 2 S. Further studies are still Anisotropic displacementp arameters hownat5 0% probability leveland hydrogen atoms omitted for clarity.…”

Synthesis and Oxidation of a Paddlewheel‐Shaped Rhodium/Antimony Complex Featuring Pyridine‐2‐Thiolate Ligands

“…Elemental analyses were carried out on aC /H/N/S analyser "Vario Micro Cube" (Elementar). [36] The NBO calculations of the Sb reference compounds were based on the X-ray structures reported for:[ (MeCÀNiPr) 2 CÀSCN] + [SbF 6 ] À , [37] OSbPh 3 , [22b] [SbPh 4 ] + [I 3 ] À , [38] [Me-CO] + [SbCl 6 ] À , [39] [PPh 4 ] + [SbBr 6 ] À , [40] [NEt 4 ] + [Sb(C 6 H 4 S 2 ) 3 ] À , [41] (bipy)SbF 3 , [42] (bipy)SbCl 3 , [43] [SbCl 5 ] 2À , [44] [HNC 5 H 4 ] + [SbCl 4 ] À , [45] SbPh 3 [46] (if applicable, positions of Ha toms were optimized prior to NBO analysis). The samples were enclosed in PMMA containers.…”

The Construction of X–CN (X=N, S, O) Bonds

“…(8)]. [32] This safe and thermally stable electrophilic group-transfer reagent can be readily synthesizedf rom dihalo(imidazolium)sulfuranes on ag ram scale.T hisc yanation protocoli s distinguished by its operational simplicity, safeness, and broad substrate scope comparedw ith other cyanating reagents,s uch as cyanogen bromideo rh ypervalent iodine reagents. (9)].…”