Cross-assembly confined bifunctional catalysis via non-covalent interactions for asymmetric halogenation

Tianyu Zheng, Rui Chen, Jingxian Huang, Theo Goncalves, Kuo-Wei Huang, Ying Yeung Yeung

Research output: Contribution to journalArticlepeer-review

17 Scopus citations

Abstract

Bifunctional catalysis plays a key role in the synthesis of useful compounds. By offering a sterically confined environment, chiral bifunctional catalysts can achieve highly enantioselective reactions. However, introducing suitable substituents to create a confined microenvironment for asymmetric catalysis on many occasions involves tedious procedures, leading to inefficient reaction optimization. Herein, we report a proof-of-concept study on formulating confined bifunctional catalysts by linking catalytic species via non-covalent interactions (NCIs). Chiral phosphate and achiral cyclopropenium cations cross-assembled to give a confined bifunctional system for asymmetric bromo-semipinacol rearrangement. By changing the achiral catalyst to aminopyridine, the system can be applied to asymmetric bromocycloetherification. These reactions are largely optimized by simply changing the achiral catalyst. A computational study revealed that the strength of the NCI donor is crucial in creating tighter catalytic pockets to amplify the effect of enantiofacial discrimination of substrates.
Original languageEnglish (US)
JournalChem
DOIs
StatePublished - Feb 13 2023

Bibliographical note

KAUST Repository Item: Exported on 2023-03-22
Acknowledgements: This study was supported by Hong Kong Special Administrative Region General Research Funding (grant no. CUHK14304918), the Chinese University of Hong Kong Direct Grant (grant no. 4053329), Croucher Foundation Senior Research Fellowship (SRF22403), and Innovation and Technology Commission to the State Key Laboratory of Synthetic Chemistry (grant no. GHP/004/16GD). The authors also acknowledge financial support and the service of Ibex, Shaheen 2 High Performance Computing Facilities from King Abdullah University of Science and Technology.

Fingerprint

Dive into the research topics of 'Cross-assembly confined bifunctional catalysis via non-covalent interactions for asymmetric halogenation'. Together they form a unique fingerprint.

Cite this