Lithiated anions derived from (alkenyl)pentamethyl phosphoric triamides: Useful synthons for the stereoselective synthesis of 9-oxo- and 10-hydroxy-2(E)-decenoic acids, important components of queen substance and royal jelly of honeybee Apis mellifera

Lithiated anions derived from (alkenyl)pentamethyl phosphoric triamides as homoenolate equivalents are used in the reaction with halogenated acetal and ketal giving regioselectively the γ-alkylation adducts. Chemoselective acidic hydrolysis of the enephosphoramide moiety in the presence of acetal or ketal groups leads to expected carbonyl products, key intermediates in the synthesis of natural compounds. The synthetic potential of the presented strategy is illustrated by stereoselective synthesis of two pheromones namely, 9-oxo-2(E)-decenoic acid 1 from queen substance and 10-hydroxy-2(E)-decenoic acid 2 from royal jelly of honeybee Apis mellifera.

Graphical abstractLithiated anions derived from (alkenyl)pentamethyl phosphoric triamides reacted with halogenated acetal and ketal giving regioselectively the γ-alkylation adducts. Chemoselective hydrolysis of the enephosphoramide moiety led to carbonyl products, key intermediates in the synthesis of pheromones, 9-oxo-2(E)-decenoic acid 1 from queen substance and 10-hydroxy-2(E)-decenoic acid 2 from royal jelly of honeybee Apis mellifera.Figure optionsDownload full-size imageDownload as PowerPoint slide