Chromium Catalyzed Asymmetric Reformatsky Reaction.
Yong-Feng LvGang LiuZhaoxin ShiZhaobin WangPublished in: Angewandte Chemie (International ed. in English) (2024)
This study describes an unprecedented chromium-catalyzed asymmetric Reformatsky reaction, enabling the synthesis of chiral β-hydroxy carbonyl compounds from α-chlorinated or α-brominated esters and amides. By employing a chiral chromium/diarylamine bis(oxazoline) catalyst, we achieved relatively broad functional group tolerance. Distinct from known reports, the protocol operates under both classical and photoredox conditions, facilitated by the in situ formation of a nucleophilic chiral chromium intermediate through a radical-polar crossover mechanism. Preliminary mechanistic insights, supported by DFT calculations, identify the nucleophilic aldehyde addition as the key stereo-determining step. This approach not only overcomes the limitations of existing Reformatsky reactions but also provides a versatile strategy for accessing complex chiral molecules.
Keyphrases
- ionic liquid
- room temperature
- capillary electrophoresis
- density functional theory
- randomized controlled trial
- mass spectrometry
- molecular dynamics
- molecular dynamics simulations
- clinical trial
- molecular docking
- gold nanoparticles
- open label
- emergency department
- solid state
- high resolution
- reduced graphene oxide
- double blind
- metal organic framework
- drug induced
- monte carlo
- tandem mass spectrometry