Stereoselectivity control in Rh-catalyzed β-OH elimination for chiral allene formation.

ABSTRACT: Stereoselectivity control and understanding in the metal-catalyzed reactions are fundamental issues in catalysis. Here we report sterically controlled rhodium-catalyzed S_N2'-type substitution reactions of optically active tertiary propargylic alcohols with arylmetallic species affording the non-readily available enantioenriched tetrasubstituted allenes via either exclusive syn- or anti-β-OH elimination, respectively, under two sets of different reaction parameters. Detailed mechanistic experiments and density functional theory (DFT) studies reveal that the exclusive anti-Rh(I)-OH elimination is dictated by the simultaneous aid of in situ generated boric acid and ambient water, which act as the shuttle in the hydroxy relay to facilitate the Rh(I)-OH elimination process via a uniq

SUBMITTER: Wang J 

PROVIDER: S-EPMC10651921 | biostudies-literature | 2023 Nov

REPOSITORIES: biostudies-literature