Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 144, Issue 30, Pages 13643-13651Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jacs.2c04043
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Funding
- National Key R&D Program of China [2021YFF0701600]
- National Natural Science Foundation of China [91856111, 21871288, 21821002, 22171280]
- CAS Youth Interdisciplinary Team [JCTD-2021-11]
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This study describes a novel method for enantioselective para-C-H activation of pyridines using a Ni-Al bimetallic catalyst system and NHC ligand, enabling the efficient synthesis of enantioenriched 1,1-diarylalkanes containing pyridine moieties.
Direct asymmetric functionalization of the pyridyl C-H bond represents a longstanding challenge in organic chemistry. We herein describe the first enantioselective para-C-H activation of pyridines through the use of a Ni-Al bimetallic catalyst system and N-heterocyclic carbene (NHC) ligand for intermolecular hydroarylation of styrenes. The reaction procceds in high to excellent enantioselectivities (up to 98.5:1.5 er) and high site-selectivities for both styrene and pyridine components (up to >98:2). Consequently, a broad range of enantioenriched 1,1-diarylalkanes containing pyridine moieties could be prepared in a single step with 100% atom economy. Computational studies supported a mechanism involving a ligand-to-ligand H-transfer (LLHT) and reductive elimination sequence, with LLHT being the rate- and enantioselectivity-determining step. DFT studies indicate that the pi-pi stacking interaction between the NHC aryl fragment and trans-styrenes is critical for high reactivity and enantiocontrol.
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