Synthesis of hypervalent iodonium alkynyl triflates for the application of generating cyanocarbenes.
The procedures described in this article involve the synthesis and isolation of hypervalent iodonium alkynyl triflates (HIATs) and their subsequent reactions with azides to form cyanocarbene intermediates. The synthesis of hypervalent iodonium alkynyl triflates can be facile, but difficulties stem from their isolation and reactivity. In particular, the necessity to use filtration under inert atmosphere at -45 °C for some HIATs requires special care and equipment. Once isolated, the compounds can be stored and used in reactions with azides to form cyanocarbene intermediates. The evidence for cyanocarbene generation is shown by visible extrusion of dinitrogen as well as the characterization of products that occur from O-H insertion, sulfoxide complexation, and cyclopropanation. A side reaction of the cyanocarbene formation is the generation of a vinylidene-carbene and the conditions to control this process are discussed. There is also potential to form a hypervalent iodonium alkenyl triflate and the means of isolation and control of its generation are provided. The O-H insertion reaction involves using a HIAT, sodium azide or tetrabutylammonium azide, and methanol as solvent/substrate. The sulfoxide complexation reaction uses a HIAT, sodium azide or tetrabutylammonium azide, and dimethyl sulfoxide as solvent. The cyclopropanations can be performed with or without the use of solvent. The azide source must be tetrabutylammonium azide and the substrate shown is styrene.
Department of Chemistry and Biochemistry, University of North Carolina at Greensboro.
I F Dempsey
IF
Hyatt
Daniel J
DJ
Nasrallah
Mitchell P
MP
Croatt
D000480:Alkynes / Q000138:chemical synthesis* / Q000737:chemistry; D001386:Azides / Q000737:chemistry; D006847:Hydrocarbons, Iodinated / Q000138:chemical synthesis / Q000737:chemistry; D008698:Mesylates / Q000138:chemical synthesis* / Q000737:chemistry; D008697:Methane / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D009570:Nitriles / Q000138:chemical synthesis* / Q000737:chemistry; D009861:Onium Compounds / Q000138:chemical synthesis* / Q000737:chemistry
D000480:Alkynes; D001386:Azides; D006847:Hydrocarbons, Iodinated; D008698:Mesylates; D009570:Nitriles; D009861:Onium Compounds; C030011:carbene; C012077:trifluoromethanesulfonic acid; D008697:Methane