A new type of binaphthyl-based chiral iodide functionalized at positions 8 and 8' of the naphthalene rings has been found as a promising structural motif for the asymmetric hypervalent iodine(III) oxidations, specifically, for the dearomatizing spirocyclization of naphthol carboxylic acids showing expectedly better enantioselectivities versus other atropisomeric biaryls, i.e., a conventionally used binaphthalene having the diiodides in the minor groove.
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http://dx.doi.org/10.1021/acs.joc.7b02037 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Dalian University of Technology, School of Chemical Engineering, No 2 Linggong Road,Ganjingzi District, 116024, Dalian, CHINA.
The Pd-catalyzed asymmetric hydrogenolysis rearrangement of allylic acetates using (s-Bu)3BHK has been described, achieving the synthesis of axially chiral alkylidene cycloalkanes with excellent enantioselectivities (up to 99% ee) and a wide substrate scope (30 examples of cyclohexanes and cyclobutanes). To the best of our knowledge, this is the first time to achieve synthesis of axially chiral olefins via asymmetric hydrogenolysis of allylic acetates. This methodology not only offers a novel synthetic pathway for non-atropisomeric axially chiral structures but also highlights the potential of asymmetric hydrogenolysis as a powerful tool in synthetic organic chemistry.
View Article and Find Full Text PDFJ Org Chem
January 2025
Chemistry and Materials Program, College of Engineering, Shibaura Institute of Technology, 3-7-5 Toyosu, Kohto-ku, Tokyo 135-8548, Japan.
Both enantiomers of 2-ethylquinazolin-4-ones bearing -CHO/CDO and CHO/CHO phenyl groups at the N3 position were prepared. These are isotopic atropisomeric compounds based on a remote and conformationally flexible H/D and C/C discrimination, and it was found that a CHCl solution of -CHO/CDO derivative shows a slight specific optical rotation. Furthermore, diastereomeric quinazolinone derivatives bearing a chiral carbon were prepared, and their stereochemical purities and rotational stability as well as the isotopic atropisomerism were verified by H NMR and chiral high-performance liquid chromatography (HPLC) analyses.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
State key laboratory for Chemistry and Molecular Engineering of Medicinal Resources, Key Laboratory for Chemistry and Molecular Engineering of Medicinal Resources (Ministry of Education of China), Collaborative Innovation Center for Guangxi Ethnic Medicine, School of Chemistry and Pharmaceutical Sciences, Guangxi Normal University, 15 Yu Cai Road, Guilin, 541004, China.
Skeletal editing represents an attractive strategy for adding complexity to a given molecular scaffold in chemical synthesis. Isodesmic reactions provide a complementary skeletal editing approach for the redistribution of chemical bonds in chemical synthesis. However, catalytic enantioselective isodesmic reaction is extremely scarce and enantioselective isodesmic reaction to synthesize atropisomeric compounds is unknown.
View Article and Find Full Text PDFMolecules
November 2024
Departamento de Química Orgánica e Inorgánica, Facultad de Ciencias, and Instituto del Agua, Cambio Climático y Sostenibilidad (IACYS)-Unidad de Química Verde y Desarrollo Sostenible, Universidad de Extremadura, 06006 Badajoz, Spain.
This publication reports a facile and convenient preparation of tri--acetyl-glucopyranoses, derived from the corresponding 2-deoxyaminosugar, where the vicinal anomeric and C2 positions are decorated by azido and (thio)ureido groups, respectively. This double functionalization leads to an inherently chiral core incorporating the versatile azido and (thio)ureido linkages prone to further manipulation. The latter also provides a structural element for hydrogen-bonded donor-acceptor (HB-DA) sites, which are of immense value in organocatalytic pursuits.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Department of Chemistry, Fudan University, 220 Handan Rd., Shanghai, 200433, China.
Atropisomers with multiple stereogenic axes have attracted much attention due to their increasing significance in the fields of natural products, chiral materials, and drug discoveries. However, the catalytic stereoselective construction of axially chiral ring scaffolds with more than two axes on a single benzene ring remains a challenging task. Herein, we present an efficient method for synthesizing triaxially chiral polysubstituted naphthalene scaffolds via sequential Ni(II)-catalyzed Diels-Alder reaction of isobenzofurans and TfOH-promoted dehydrative aromatization reaction.
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