ORGANOBORANES FOR SYNTHESIS. 10. THE BASE-INDUCED REACTION OF BROMINE WITH ORGANOBORNES. A CONVENIENT PROCEDURE FOR THE CONVERSION OF ALKENES INTO ALKYL BROMIDES VIA HYDROBORATION

Article abstract of DOI:10.1016/S0040-4020(88)90012-9

The reaction of trialkylboranes with bromine is greatly accelerated by base.Bromination in the presence of sodium hydroxide provides alkyl bromide along with a large amount of the corresponding alcohol.The use of sodium methoxide as a base eliminates this undesirable side reaction and provides an improved yield of alkyl bromide.Consequently, hydroboration, followed by bromination in the presence of sodium methoxide, provides a convenient new procedure for the conversion of alkenes into alkyl bromides.The organoboranes, obtained via hydroboration of terminal alkenes, react with the utilization of all three alkyl groups attached to boron, providing nearly quantitative yields of alkyl bromides. This procedure also accommodates common organic functional groups, as demonstrated by the preparation of methyl 11-bromoundecanoate and 11-bromoundecyl acetate from the corresponding functionally substituted alkenes.Under these conditions, secondary and bulky primary alkyl groups react more sluggishly.However, a procedure involving simultaneous addition of bromine and methanolic sodium methoxide provides improved results for such derivatives.Surprisingly, the base-induced bromination of tri-exo-nobornylborane results in an inversion of configuration at the reaction center to give predominantly endo-2-bromonorbornane.A mechanism is proposed to account for this remarkable inversion.