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We report an ether-directed enantioselective C(sp)-H borylation catalyzed by a chiral bidentate boryl ligand (CBL)/iridium system for constructing axially chiral biaryls. This method delivered diverse chiral biaryls with good to high enantioselectivities, accommodating varied electronic and steric substituents on the aryl rings. Gram-scale synthesis and downstream transformations of the C-B bond underscored its practicality.
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http://dx.doi.org/10.1021/acs.orglett.5c00919 | DOI Listing |
Org Lett
September 2025
Chengdu Institute of Organic Chemistry, Chinese Academy of Sciences, Chengdu, Sichuan 610093, P. R. China.
The first enantioselective Bora-Brook rearrangement reaction catalyzed by a Cu/SOP system was established. In this protocol, the synthesis of axially chiral monoaldehydes has been achieved by the desymmetric reduction of prochiral dialdehydes. This reaction proceeds smoothly under mild conditions, affording the products in high yields (up to 91%) with excellent enantioselectivities (up to 96:4 er) while exhibiting broad functional group compatibility.
View Article and Find Full Text PDFInt J Mol Sci
August 2025
Department of Organic Chemistry, University of Debrecen, P.O. Box 400, 4002 Debrecen, Hungary.
Inspired by naturally occurring -isochromans such as penicisteckins, we envisaged the first synthesis of biaryl-type -1-arylisochromans containing a stereogenic -trisubstituted biaryl axis. We achieved the stereoselective synthesis of 5,5'-linked heterodimeric -isochromans containing both central and axial chirality elements by performing diastereoselective Suzuki-Miyaura biaryl coupling reactions on two optically active 1-arylpropan-2-ol derivatives, followed by two oxa-Pictet-Spengler cyclizations with aryl aldehydes or methoxymethyl chloride. We studied the diastereoselectivity of the cyclization step, separated the stereoisomeric products with chiral preparative HPLC and determined the absolute configuration through a combination of vibrational circular dichroism (VCD), NMR and single-crystal X-ray diffraction analysis.
View Article and Find Full Text PDFChemMedChem
August 2025
Pharmaceutical/Medicinal Chemistry, Institute of Pharmacy, University of Greifswald, Friedrich-Ludwig-Jahn-Str. 17, 17489, Greifswald, Germany.
Binaphthyls usually serve as key chiral ligands in catalysts for asymmetric syntheses, having been reported in thousands of published reactions. Herein, the discovery that atropisomeric (R)-[1,1'-binaphthalene]-2,2'-diamine (R-BINAM, 1(R)) is a moderately potent spindle poison, causing antiproliferation, depolymerization of microtubules, multipolar spindles, pericentriolar material (PCM) fragmentation, mitotic catastrophe, multinucleated cells, and apoptosis in cancer and normal human cell lines, is reported. Furthermore, the resulting abnormalities resemble those induced by microtubule-depolymerizing agents (MDAs) such as colchicine.
View Article and Find Full Text PDFJ Am Chem Soc
August 2025
Institut für Chemie, Technische Universität Berlin, Straße des 17. Juni 115, 10623 Berlin, Germany.
A kinetic resolution of racemic biaryl monotriflates by an atroposelective palladium-catalyzed diazenylation enables the synthesis of azobenzene derivatives decorated with an axially chiral substituent. The C(sp)-N(sp) cross-coupling reaction makes use of silylated diazenes as diazenyl anion equivalents, and chiral ferrocene-based bisphosphine ligands act as effective supporting ligands. The resulting chiral azobenzenes bearing binaphthyl and naphthyl/phenyl backbones undergo reversible - isomerization under irradiation with LEDs of different wavelengths, highlighting their potential use in photoresponsive chiroptical materials.
View Article and Find Full Text PDFOrg Lett
August 2025
College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, China.
1,1'-Biaryls are a class of axially chiral compounds, while π-extension with nonbenzenoid rings has been less known. Herein, we report a π-extended 1,1'-binaphthyl containing a nor[5]helicene skeleton. The synthesis was performed via an intermolecular SAr-type reaction of 5,11-di(naphthalen-2-yl)tetracene.
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