Synthesis and Palladium-Catalyzed Cross-Coupling of an Alkyl-Substituted Alkenylboronic Acid Pinacol Ester with Aryl Bromides

The palladium-catalyzed cross-coupling reaction of alkyl-substituted alkenylboron reagents with aryl halides is a versatile method to introduce a hydrophobic hydrocarbon chain onto organic compounds of interest. The application of the cross-coupling reaction is enabled by synthetic methods for the preparation of alkenylboron reagents. The geometrically pure, alkyl-substituted alkenylboron reagent, (E)-octenylboronic acid pinacol ester, was prepared by 9-BBN-catalyzed hydroboration reaction of 1-octene with pinacolborane in refluxing 1 M THF solution. This reagent was then evaluated in palladium-catalyzed cross-coupling reactions with aryl bromides. The highest yield of the (E)-1-phenyloctene was obtained when SPhos was used as the ligand, K2CO3 was used as the base, and DMF was used as the reaction solvent. Other electron-rich, electron-poor, sterically hindered, and heteroaromatic substrates produced the corresponding (E)-1-phenyloctene derivatives in moderate to good yield. KEYWORDS: Organic synthesis; Aryl alkene synthesis; Palladium-catalyzed cross-coupling; Suzuki-Miyaura reaction; Stereocontrolled alkene preparation; Hydroboration; 9-Borobicyclo[3.3.1]nonane; Reaction optimization