Rhodium-catalyzed atropodivergent hydroamination of alkynes by leveraging two potential enantiodetermining steps

• DOI: 10.1126/sciadv.adr4435
• Publication Date: 2024-11-27T19:01:25Z
• Authors: Ruijie Mi; Rongkai Wu; Jierui Jing; Fen Wang; Xiao-Xi Li; Xin Hong; Xingwei Li
• Keywords: Hydroamination; Protonolysis; Alkyne; Chirality

A pair of enantiomers is known to have different biological activities. Two catalysts with opposite chirality are nearly always required deliver both enantiomeric products. In this work, chiral rhodium(III) cyclopentadienyl complexes repurposed as efficient for enantiodivergent and atroposelective hydroamination sterically hindered alkynes. Products been obtained using the same or closely analogous catalyst in good efficiency excellent enantioselectivity, enantiodivergence was mainly enabled by an achiral carboxylic acid its silver salt. Mechanistic studies revealed origin ascribable switch enantiodetermining step (alkyne insertion versus protonolysis) under control, which constitutes a previously unidentified working mode leveraging two elementary steps.