A novel stereoselective and catalytic CC coupling reaction: acetylene dimerization accompanied by addition of iodine to yield (E,E)-1,4-diiodobuta-1,3-diene in the PtIV–I––I2–MeOH system

Highly Selective Catalytic Synthesis of (E,E)-1,4-Diiodobuta-1,3-diene via Atom-Efficient Addition of Acetylene and Iodine: A Versatile (E,E)-1,3-Diene Building Block in Cross-Coupling Reactions

“…7 The reaction required as much as 0.25 equivalents of Pt salt and resulted in ca. 90-95% purity of product.…”

Mechanochemistry in heterogeneous catalysis

“…By analogy with the homogeneous transformations of acetylene [96,97] it was suggested that heterogeneous hydrochlorination also takes place through the intermediate formation of a b-halogenovinyl derivative of platinum(IV). In fact, the formation of the b-chlorovinyl complex Pt IV -CH=CHCl (I) under heterogeneous conditions was demonstrated by NMR [113].…”

“…Under homogeneous conditions the acid complexes of platinum(II) and platinum(IV) catalyze a series of transformations of various types of hydrocarbons and their derivatives. The chloride complexes of platinum(II) realize the catalytic functionalization of saturated and aromatic hydrocarbons [92][93][94]; the iodide complexes of platinum(II) catalyze the hydroiodination of ethylene to ethyl iodide [95], while those of platinum(IV) in acidic solutions catalyze the hydroiodination of acetylene to vinyl iodide [96] and, in neutral solution, the dimerization of acetylene, accompanied by the addition of iodine with the formation of (E,E)-1,4-diiodo-1,3-butadiene [97]. The chloride complexes of platinum, deposited on silica gel, also activate alkanes under heterogeneous conditions [98].…”

Iridium-catalyzed hydroiodination of functionalized alkynes

“…To the best of our knowledge, the groups of Campos, Rodriguez and Mitchenko described unique catalytic systems based on either a mixture of iodine, CuO.HBF 4 (50 mol%) and triethylsilane or a platinum(IV) catalyst [16,17]. Mitchenko, Beletskaya and co-workers reported the Pt-catalyzed dimerization of acetylene, which was accompanied by addition of iodine and which led to (E, E)-1,4-diiodobuta-1,3-diene [18]. The preparation of vinyliodides still requires investigation for functionalized substrates, which are non-compatible with the classical methods.…”