Halomethoxylation of monoterpenes using (dichloroiodo)benzene

Abstract

Reactions of (dichloroiodo)benzene or (dichloroiodo)benzene/iodine with various monoterpenes in methanol provide a selective approach to the respective products of chloromethoxylation or iodomethoxylation of the double bond. The halomethoxylation of (+)-3-carene, carvone, and β-pinene proceeds with especially high regio- and stereoselectivity affording an appropriate single product in each case, while the reaction of limonene gives products of functionalization of both double bonds. This new methodology for the controlled introduction of halogen substituents into the structure of naturally occuring monoterpenes provides an entry into various potentially important synthetic intermediates. © ARKAT.