Nickel-catalyzed Suzuki-Miyaura reactions of unactivated halides with alkyl boranes and planar-chiral borabenzene catalysts for Diels-Alder reactions

Abstract

Part I describes the expansion in scope of a nickel-catalyzed coupling reaction of unactivated alkyl bromides and alkyl boranes to include unactivated alkyl chlorides. The new method is adapted for use outside of a glove box and is also found to be applicable not only to the coupling of primary chlorides, but also to the coupling of bromides and iodides, both primary and secondary. ... This coupling reaction of chlorides is further adapted to the of p-chloro aryl alkyl amines. This work constitutes an extension directing groups for the asymmetric Suzuki-Miyaura reactions halides. ... Part II details work towards an asymmetric Diels-Alder reaction between cyclopentadiene and methacrolein catalyzed by a planar-chiral boron Lewis acid. This system exhibits a level of turnover that is unprecedented in reactions mediated by planar chiral boron heterocycles. Computational studies shed light on the nature of the 7tsymmetry interaction between borabenzenes and complexed carbonyl groups. The selectivity of the borabenzene-catalyzed Diels-Alder reaction is also examined.