Mn(II)-Catalyzed Markovnikov Hydroiodination of Terminal Aryl Alkynes.

A Mn(II)-catalyzed Markovnikov hydroiodination of terminal aryl alkynes with TMSI as the iodination reagent has been developed. Cheap Mn(OAc)2·4H2O was employed as the catalyst. Twenty-five aryl alkynes (including two internal alkynes) were successfully transformed into their α-iodide styrene derivatives, including those natural product-based alkynes and poly alkynyl benzenes. The reaction has good chemoselectivity of alkynes over alkenes, which enabled the tolerance of olefin in the substrate. Gram-scale synthesis was also conducted.

Lewis acid catalyzed Markovnikov hydrobromination and hydrochlorination of alkynes using TMSX (X = Br, Cl).

Markovnikov hydrobromination and hydrochlorination of alkynes were achieved using TMSX (X = Br, Cl) instead of corrosive HX (X = Br, Cl) as the bromination and chlorination reagents. Mn(OAc)2·4H2O was used as the hydrobromination catalyst for electron-neutral/rich alkynes. For the hydrobromination of electron-deficient alkynes and hydrochlorination of alkynes, Zn(OAc)2·2H2O was employed as the catalyst. Mechanistic studies suggested that the in situ formed TMS-substituted alkyne might be a reactive intermediate and the proton of the terminal alkyne should be a hydrogen source for the hydrohalogenation reaction.