Copper-Catalyzed Cross- and Carbonylative Coupling Reactions of ­Alkynyliodonium Salts with Organoboronic Acids and Organostannanes

Abstract

Copper-catalyzed cross-and carbonylative coupling reactions have been achieved in the reaction of a variety of alkynyliodonium salts with arylboronic acids and organostannanes under the mild reaction conditions in high yield. Our investigation shows that the alkynylidonium tetrafluoroborates are more efficient than those of triflates and tosylates.

Transition metals in organic synthesis: Highlights for the year 2005

“…11 C-Labelled aryl alkyl ketones were prepared from organic iodides, 11 C-labeled carbon monoxide and organotin reagents [515]. Copper catalyzed carbonylative crosscouplings of alkynyl iodonium salts with organostannanes in the presence of carbon monoxide [516]. A palladium-catalyzed carbonylative coupling of 3-iodoindoles with a terminal alkyne was used in a synthesis of meridianines [517].…”

Nucleophilic fluorination of alkynyliodonium salts by alkali metal fluorides: access to fluorovinylic compounds

“…Alkynyliodonium tosylates 1b and 1g were prepared from the corresponding terminal alkynes and the PhI(OH)OTs at room temperature, according to the Koser's method. 18,19 Alkynyliodonium tetrafluoroborate salts 1a,cef were synthesized from terminal alkynes and PhIO at 0 C or at room temperature as the procedure of Yoshida et al 20 The spectral data of 1a [n-hexynyl(phenyl)iodonium tetrafluoroborate], 21 19 have been previously reported in the literature. Products were characterized by comparison with these data.…”

Alkynylation with Hypervalent Iodine Reagents

“…Through the right choice of the organometallic reagent (organocopper or cuprate), the reaction was successful on sp [43], sp 2 [44], and sp 3 [43,45] centers to give diynes, enynes and aliphatic alkynes as products. Due to their high reactivity, alkynyliodonium salts have also found applications in palladium-or coppercatalyzed alkynylation reactions such as carbonylation [46], Heck coupling [47][48], reactions with alkynes [49] and cross-coupling with organoboron/tin compounds [50]. However, their use in these transformations remains scarce, probably due their somewhat low stability in the presence of transition metals and the availability of more convenient alkyne sources.…”