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An efficient enantioselective coupling reaction between sulfenamides and cyclic diaryliodonium salts is established via adaptive Cu/anionic stereogenic-at-Co(III) complex combined catalysis, precisely synthesizing a broad range of axially chiral sulfilimines with excellent enantioselectivities, diastereoselectivities, regioselectivities, and chemoselectivities (67 examples under same conditions, up to 98 % ee). The following thermodynamically controlled pyramidal inversion enables efficient stereodivegent synthesis of all four stereoisomers. Mechanistic studies suggest that anionic stereogenic-at-cobalt(III) complexes serve as counteranions of diaryliodonium and anionic ligand of Cu(I) catalyst simultaneously, which could be regarded as an explanation for outstanding selectivities.
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http://dx.doi.org/10.1002/anie.202419596 | 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 PDFJ Am Chem Soc
August 2025
Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education of China, Key Laboratory of the Assembly and Application of Organic Functional Molecules of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 4100
While the conversion of simple cyclic ketones to lactams via carbon-carbon (C-C) bond cleavage can be accomplished through classical Beckmann and Schmidt rearrangements, these methods suffer from inherent limitations. Beyond regioselectivity challenges, they permit the incorporation of only a single nitrogen atom into the parent carbocyclic framework. Herein, an efficient approach to access medium-to-large sized lactams was developed through an alkyne migratory insertion enabled C-C bond activation of unstrained ketones.
View Article and Find Full Text PDFOrg Lett
September 2025
Key Laboratory of Functionalized Molecular Solids, Ministry of Education, Anhui Key Laboratory of Molecule-Based Materials (State Key Laboratory Cultivation Base), College of Chemistry and Materials Science, Anhui Normal University, Wuhu 241002, Anhui, China.
We present here a chiral phosphoric acid-catalyzed asymmetric Doyle indolization enabling efficient construction of axially chiral indolizinylindoles with stable C-N stereogenic axes. Importantly, this intriguing cascade cyclization realized the highly enantioselective synthesis of axially chiral quarteraryl skeletons containing two contiguous stereogenic axes in good to high yields and excellent stereoselectivities. Furthermore, an atropo-divergent synthesis was achieved via switching the 3,3'-substituents of the CPA catalyst.
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.
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