3,3'-di(2-pyridyl) BINOLs (4), prepared in three steps from commercial substances by a combined directed ortho metalation-Negishi cross-coupling protocol, constitute new members of the BINOL ligand family. They are among the most selective, general ligands, providing equal or greater stereoselectivities in the Et2Zn addition to benzaldehydes and cinnamaldehydes (Table 3) than any single BINOL ligand reported to date.
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http://dx.doi.org/10.1021/ol071276f | DOI Listing |
Inorg Chem
January 2025
Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, United States.
Luminescent chiral metal-organic frameworks (CMOFs) are promising candidates for the enantioselective sensing of important chiral molecules. Herein, we report the synthesis and characterization of Zn and Cd CMOFs based on 1,1'-bi-2-naphthol (BINOL)-derived 3,3',6,6'-tetra(benzoic acids), H-OEt and H-OH. Four CMOFs, -OEt, -OH, -OEt, and -OH, based on these ligands were crystallographically characterized.
View Article and Find Full Text PDFNat Commun
January 2025
State Key Laboratory of Coordination Chemistry, Key Laboratory of Mesoscopic Chemistry of Ministry of Education, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, China.
Chiral binaphthols (BINOL)-metal combinations serve as powerful catalysts in asymmetric synthesis. Their chiral induction mode, however, typically relies on multifarious non-covalent interactions between the substrate and the BINOL ligand. In this work, we demonstrate that the chiral-at-metal stereoinduction mode could serve as an alternative mechanism for BINOL-metal catalysis, based on mechanistic studies of BINOL-aluminum-catalyzed asymmetric hydroboration of heteroaryl ketones.
View Article and Find Full Text PDFJ Org Chem
January 2025
State Key Laboratory of Medicinal Chemical Biology, College of Pharmacy and Tianjin Key Laboratory of Molecular Drug Research, Nankai University, Tianjin 300350, China.
Here, we demonstrated a copper(II)-catalyzed enantioselective addition of aryl amines to isatin-derived -Boc-ketimines using chiral O-N-N tridentate ligands derived from BINOL and proline. Generally, the chiral acyclic ,'-ketals were obtained in high yields (up to 98%) and excellent ee values (up to 98%). Various aryl amines could be tolerated and a gram-scale reaction was also possible.
View Article and Find Full Text PDFInorg Chem
December 2024
Center of Advanced Analysis and Gene Sequencing, Key Laboratory of Molecular Sensing and Harmful Substances Detection Technology, Zhengzhou University, Kexue Avenue 100, Zhengzhou, Henan 450001, P. R. China.
The enantioselective performance of porous chiral metal-organic frameworks (CMOFs) is closely related to the pore size and uniformity of easily accessible active sites. The chiral recognition efficiency of microporous CMOFs is hindered by the restricted diffusion of the guest. Hierarchical porous chiral CMOFs with multiple pore size regimes ranging from micropores to macropores have emerged as potential candidates in chiral separation applications.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Department of Chemistry, Pohang University of Science and Technology (POSTECH), Pohang 37673, Republic of Korea.
We report a copper-catalyzed regio-, diastereo-, and enantioselective allylic alkylation of allyl bromides using 1,1-diborylalkanes as prochiral nucleophiles. This methodology employs copper(I) bromide as a catalyst, an ()-BINOL-derived phosphoramidite as a ligand, and lithium benzoate as a crucial additive. The reaction affords enantioenriched homoallylic boronic esters possessing vicinal stereocenters in good yields and high diastereo- and enantioselectivity.
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