Diastereodivergent Synthesis of Trisubstituted Alkenes through Protodeboronation of Allylic Boronic Esters: Application to the Synthesis of the Californian Red Scale Beetle Pheromone

• Published in: Angewandte Chemie International Edition Vol. 51; no. 50; pp. 12444 - 12448
• Main Authors: Hesse, Matthew J., Butts, Craig P., Willis, Christine L., Aggarwal, Varinder K.
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 07.12.2012; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: alkenes; Alkenes - chemical synthesis; Alkenes - chemistry; allylic compounds; Animals; Benzenesulfonates - chemistry; Biological Products - chemistry; Biological Products - metabolism; Boron - chemistry; Catalysis; Chemistry; Chemistry, Multidisciplinary; Coleoptera - metabolism; Copper - chemistry; diastereoselectivity; Esters; Hydrofluoric Acid - chemistry; Light; natural products; Physical Sciences; Potassium Compounds - chemistry; protodeboronation; Science & Technology; Sex Attractants - chemistry; Sex Attractants - metabolism; Stereoisomerism; CONVERSION; protodeboronation; STEREOSPECIFIC SYNTHESIS; ALDEHYDES; diastereoselectivity; alkenes; SEX-PHEROMONE; ALCOHOLS; REARRANGEMENT; natural products; OLEFINATION REACTION; allylic compounds; HIGHLY STEREOSELECTIVE-SYNTHESIS; SELECTIVITY; BORYLATION
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201207312

E‐allylic boronic esters undergo a highly diastereoselective protodeboronation with TBAF⋅3 H2O to give Z‐trisubstituted alkenes. The selectivity can be switched to give predominantly the E‐alkene instead by using KHF2/TsOH (see scheme). The utility of the methodology has been illustrated in a short synthesis of a component of the sex pheromone of the Californian red scale beetle.