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Updated: Jun 13, 2026
Chemoselective Preparation of 1-Iodoalkynes, 1,2-Diiodoalkenes, and 1,1,2-Triiodoalkenes Based on the Oxidative Iodination of Terminal Alkynes
Published on: September 12, 2018
Alkyne activation with Brønsted acids, iodine, or gold complexes, and its fate leading to synthetic application
Yoshinori Yamamoto1, Ilya D Gridnev, Nitin T Patil
1Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan. yoshi@mail.tains.tohoku.ac.jp
Abstract:
The reaction of 2-alkynyl-1-methylene azide aromatics 1 with iodine gives 1,3-disubstituted 4-iodoisoquinolines 3, and the treatment of 1 with a gold-silver combined catalyst affords isoquinolines 4. On the other hand, TfOH-catalyzed reaction of 1 produces 1,3-dipolar cycloadducts, triazoles 5. Computations reveal that non-symmetrical and slightly non-symmetrical coordinations between the triple bond and electrophiles (cationic Au and iodonium species) are prone to give the isoquinolines, while symmetrical coordination with electrophiles (a Brønsted acid and Au(I)) affords the triazoles. Keeping this background material in mind, the reactions through alkyne activation with electrophiles are surveyed. In most cases, products having similar structural frameworks were obtained through alkyne activation with Brønsted acids, iodine and gold complexes; the difference is whether H or I is incorporated in the final products. However, in a few cases, different reactivities and product structures were observed between those three reagents and catalysts.
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The acidic strength of hydrocarbons follows the order: Alkynes > Alkenes > Alkanes. The strength of an acid is commonly expressed in units of pKa — the lower the pKa, the stronger the acid. Among the hydrocarbons, terminal alkynes have lower pKa values and are, therefore, more acidic. For example, the pKa values for ethane, ethene, and acetylene are 51, 44, and 25, respectively, as shown here.
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