New Approache for Gem-Dihalids and Their Applications

Kseniya Kulbitski, Schulich Faculty of Chemistry, Technion – Israel Institute of Technology, Haifa, Israel
Xiaojian Jiang, Schulich Faculty of Chemistry, Technion – Israel Institute of Technology, Haifa, Israel
Sakthivel Sekarpandi, Schulich Faculty of Chemistry, Technion – Israel Institute of Technology, Haifa, Israel
Gennady Nisnevich, Schulich Faculty of Chemistry, Technion – Israel Institute of Technology, Haifa, Israel
Mark Gandelman, Schulich Faculty of Chemistry, Technion – Israel Institute of Technology, Haifa, Israel

The rich chemistry of the carbon-iodine bond has made it a particularly rewarding synthetic tool of routine use for the purpose of functional group interconversion. Novel methodologies for efficient synthesis of organic iodides is an important goal in organic chemistry. Recently, we developed a novel, general and robust method for the conversion of aliphatic and aromatic carboxylic acids to organic iodides without the use of heavy metals or strong oxidizing agents. Commercially available N-iodoamides were used for both initiation and halogen donation under irradiative conditions. Isolation of the product is extremely simple and the major co-product is removed as a water-soluble biodegradable material. This new methodology was further applied to the successful synthesis of geminal diiodo- and iodohalo-compounds (halo = Br, Cl, F). ^[1]

Organic iodides have been recognized as valuable synthons or precursors in organic synthesis, particularly carbon–carbon, carbon–nitrogen, carbon–oxygen or carbon–sulfur bond formation. Here, we demonstrate that iodo, halo-compounds, prepared by our methodology, can be used direct synthesis of valuable organic products. For example, geminal iodo, fluoro-alkanes are utilized in metal mediated cross-coupling reactions to efficiently result in secondary organic fluorides. This approach allows for site-selective fluorination of non-activated alkyl chains, and synthesis of tailor-made secondary organic fluorides. ^[2]

^[1] K. Kulbitski; G. Nisnevich; M. Gandelman, Adv. Synth. Catal. 2011, 353, 1438.

^[2] X. Jiang, S. Sakthivel, K. Kulbitski, G. Nisnevich, M. Gandelman, J. Am. Chem. Soc., 2014, 136, 9548