In this manuscript, we portrayed a stereospecific synthesis of - and -symmetric pyrene-fused [7]helicene compounds and , respectively. Compounds and were synthesized via a one-pot Suzuki coupling-C-H activation and two-step Suzuki coupling-Scholl reaction, respectively, with complete retention of configuration. The synthesized molecules differ in the fusing mode of [7]helicene units with pyrene via six- and seven-membered rings for and , respectively. There was a significant difference in the functional properties and enantiomerization barrier of both compounds because of their distinct molecular symmetry as well as fusing mode to pyrene moiety. The heptagon-containing molecule showed remarkable photophysical and chiroptical properties with commendable configurational stability compared to and pristine [7]helicene as well as its [5]helicene congener.
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http://dx.doi.org/10.1021/acs.joc.1c02281 | DOI Listing |
Nat Commun
January 2025
Shenzhen Grubbs Institute and Department of Chemistry, Shenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, Guangdong, China.
3-Amino boron dipyrromethenes (BODIPYs) are a versatile class of fluorophores widely utilized in live cell imaging, photodynamic therapy, and fluorescent materials science. Despite the growing demand for optically active BODIPYs, the synthesis of chiral 3-amino-BODIPYs, particularly the catalytic asymmetric version, remains a challenge. Herein, we report the synthesis of boron-stereogenic 3-amino-BODIPYs via a palladium-catalyzed desymmetric C-N cross-coupling of prochiral 3,5-dihalogen-BODIPYs.
View Article and Find Full Text PDFBiochemistry
January 2025
Division of Food Science and Biotechnology, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan.
CYP105A1 exhibits monooxygenase activity to a wide variety of structurally different substrates with regio- and stereospecificity, making its application range broad. Our previous studies have shown that CYP105A1 wild type and its variants metabolize 12 types of nonsteroidal anti-inflammatory drugs (NSAIDs). In particular, the R84A variant exhibited a high activity against many NSAIDs.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Applied Chemistry, Anhui Province Engineering Laboratory for Green Pesticide Development and Application, and Anhui Province Key Laboratory of Crop Integrated Pest Management, Anhui Agricultural University, Hefei 230036, China.
Asymmetric catalysis involving a sulfoxide electrophile intermediate presents an efficient methodology for accessing stereogenic-at-sulfur compounds, such as sulfinate esters, sulfinamides, , which have garnered increasing attention in modern pharmaceutical sciences. However, as the aza-analog of sulfoxide electrophiles, the asymmetric issues about electrophilic sulfinimidoyl species remain largely unexplored and represent a significant challenge in sulfur stereochemistry. Herein, we exhibit an anionic stereogenic-at-cobalt(III) complex-catalyzed asymmetric synthesis of chiral sulfinamides via chiral sulfinimidoyl iodide intermediates.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Xi'an Jiaotong University, School of Chemical Engineering & Technology, Xingqing Road 28, 710049, Xi'an, CHINA.
The nickel catalyzed multi-component cross-electrophile carbonylation which emerges as a powerful and efficient method for constructing diverse ketones has attracted increasing attention of organic chemists. However, the selectivity of this reaction poses a significant challenge. In this work, we have developed a current-regulated selective nickel-catalyzed electroreductive cross-electrophile carbonylation, which offers a direct convergent synthesis of β/γ-hydroxy ketones, which represent pivotal structural motifs found in numerous natural products, bioactive molecules, pharmaceutical compounds, and essential building blocks.
View Article and Find Full Text PDFJ Nat Prod
December 2024
Institut für Pharmazeutische Biologie und Biotechnologie, Fachbereich Pharmazie, Philipps-Universität Marburg, Robert-Koch-Straße 4, Marburg 35037, Germany.
A three-gene cluster from was proven to be responsible for the formation of -l-Trp-l-Leu (cWL) derivatives. An strain harboring the cyclodipeptide synthase (CDPS) gene produced cWL. Expression of the whole cluster or genes of various combinations in revealed different metabolites of cWL by two cytochrome P450 enzymes.
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