Gold-catalysed asymmetric net addition of unactivated propargylic C-H bonds to tethered aldehydes.

ABSTRACT: The asymmetric one-step net addition of unactivated propargylic C-H bond to aldehyde leads to an atom-economic construction of versatile chiral propargylic alcohols but has not been realized previously. Here we show its implementation in an intramolecular manner under mild reaction conditions. Via cooperative gold catalysis enabled by a chiral bifunctional phosphine ligand, this chemistry achieves asymmetric catalytic deprotonation of propargylic C-H (pK_a > 30) by a tertiary amine group (pK_a ~ 10) of the ligand in the presence of much more acidic aldehydic α-hydrogens (pKa ~ 17). The reaction exhibits a broad scope and readily accommodates various functional groups. The 5-/6-membered ring fused homopropargylic alcohol products are formed with excellent enantiomeric ex

SUBMITTER: Li T 

PROVIDER: S-EPMC8574197 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature