Preparation and synthetic application of vinylic tellurides and vinyltins

Abstract

Hydrozirconation of acetylenic tellurides afforded 1,1-bimetalloalkenes of tellurium and zirconium. The intermediates were converted to ketene organyltelluroacetals after treatment with organyltellurenyl iodide. In a matter of days products in solution were decomposed to an insoluble white powder and other organic compounds. The butylphenyltelluro acetal was decomposed into complicated mixtures. 1-Substituted (1E,3E)-1,3-butadienyl phenyl tellurides and internal vinylic tellurides were synthesized by the highly regio- and stereo- selective one-pot method. They could be very useful intermediates in synthesis of 1,3-dienyl moieties that are encountered as main part-structures of many natural products such as insect pheromones. We used electrophile-induced rearrangement of borates and PhTeI that accomplished the preferential migration of the alkenyl or alkyl group from boron to the adjacent alkynyl sp- carbon. A electrophile-induced rearrangement of lithium 1- octynylborate with suitably bulk electrophile Me3SnCl was used in the synthesis of the (3E,5Z)-3,5-dodecadienyl acetate that is a sex pheromone of the leafroller moth Phtheochroa cranaodes Meyrick (Lepidoptera: Tortricidae). The required (3E)- stereochemistry of the sex pheromone was easily obtained by regio- and stereo-selective hydroboration of alkyne.