ChemInform Abstract: Samarium(II) Iodide-Induced Reductive Cyclization of Unactivated Olefinic Ketones. Sequential Radical Cyclization/Intermolecular Nucleophilic Addition and Substitution Reactions

Samarium (II) iodide in the presence of HMPA effectively promotes the intramolecular coupling of unactivated olefinic ketones by a reductive ketyl-olefin radical-cyclization process. The reaction is quite for the formation of 5- and 6-membered carbocycles and even provides modest yields in less facile cyclization processes as evidenced by the generation of methylcyclooctanol via an 8-endo cyclization. Sequential radical cyclization-intermolecular nucleophilic addition/substitution process set the SmI 2 reaction apart from its radical-chain,photochemical, and electrochemical counterparts