REACTION OF GRIGNARD REAGENTS WITH DIISOPROPYL-AMINOBORANE. SYNTHESIS OF ALKYL, ARYL, HETEROARYL AND ALLYL BORONIC ACIDS FROM ORGANO(DIISOPROPYL)- AMINOBORANE BY A SIMPLE HYDROLYSIS

摘要

Diisopropylaminoborane (BH2-N(iPr)2) is prepared by reacting lithium diisopropylaminoborohydride (iPr-LAB) with trimethylsilyl chloride (TMSC1). Aliphatic, aromatic, and heteroaromatic (diisopropylamino)boranes are readily synthesized at ambient temperature (0 °C) in 1 h by the reaction of Grignard reagents with (BH2-N(7Pr)2). Two contending reaction pathways have tentatively been identified. During the mechanistic investigation, bromomagnesium diisopropylaminoborohydride was identified as a byproduct. This borylation reaction can be carried out under Barbier conditions, where (BH2-N(iPr)2) traps the in situ formed Grignard reagent from the corresponding organic halide and magnesium metal. Simple acid hydrolysis of the product organo(diisopropylamino)borane leads to the corresponding boronic acid in good to excellent yield.