A highly enantioselective synthesis of substituted tetrahydrocarbolines via Ir-catalyzed Friedel-Crafts type intramolecular asymmetric allylic alkylation of 2-indolyl allyl carbonates has been developed. This strategy features excellent chemoselectivity and enantioselectivity, mild reaction conditions, and an easily accessed chiral ligand.
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http://dx.doi.org/10.1021/ol4027717 | DOI Listing |
Sci Bull (Beijing)
December 2024
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, China. Electronic address:
Divergent synthesis of valuable molecules through common starting materials and metal catalysis represents a longstanding challenge and a significant research goal. We here describe chemodivergent, highly enantio- and regioselective nickel-catalyzed reductive and dehydrogenative coupling reactions of alkynes, aldehydes, and silanes. A single chiral Ni-based catalyst is leveraged to directly prepare three distinct enantioenriched products (silyl-protected trisubstituted chiral allylic alcohols, oxasilacyclopentenes, and silicon-stereogenic oxasilacyclopentenes) in a single chemical operation.
View Article and Find Full Text PDFAdv Mater
December 2024
School of Chemistry and Chemical Engineering and State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, Shanghai, 200240, China.
Asymmetric catalysis is essential for addressing the increasing demand for enantiopure compounds. Recent advances in reticular chemistry have demonstrated that metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) possess highly regular porous architectures, exceptional tunability, and the ability to incorporate chiral functionalities through their open channels or cavities. These characteristics make them highly effective and enantioselective catalysts for a wide range of asymmetric transformations.
View Article and Find Full Text PDFAdv Sci (Weinh)
December 2024
Department of Orthopedics, Shanghai Sixth People's Hospital Affiliated to Shanghai Jiao Tong University School of Medicine, Shanghai, 200233, P. R. China.
Inspired by the fundamental attribute of chirality in nature, chiral-engineered biomaterials now represent a groundbreaking frontier in biomedical fields. However, the integration of chirality within inorganic materials remains a critical challenge and developments of chirality-induced bionic bone implants are still in infancy. In this view, novel chiral hydroxyapatite (CHA) coated Ti alloys are successfully synthesized by a sophisticated chiral molecule-induced self-assembly method for the first time.
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China.
Compared with chiral β-amino phosphorus compounds, which can be easily derived from natural optically pure α-amino acids, obtaining chiral β-amino phosphorus derivatives remains a challenge. These derivatives, which cannot be derived from chiral natural amino acids, possess unique biological activities or potential catalytic activities. Herein, highly enantioselective hydrogenation for the preparation of chiral β-amino phosphorus derivatives from -β-enamido phosphorus compounds is reported by using a green and low-cost earth-abundant metal nickel catalyst (13 examples of 99% ee).
View Article and Find Full Text PDFJ Am Chem Soc
December 2024
State Key Laboratory of Chemical Biology, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032, China.
Here, we report the enantioselective total syntheses of four diepoxy--kaurane diterpenoids including (-)-Macrocalin B, (-)-Acetyl-macrocalin B, and (-)-Isoadenolin A and the revised structure of (-)-Phyllostacin I, which hinges on the strategic design of a regioselective and stereospecific trapping of a highly reactive [3.2.1]-bridgehead enone intermediate via a tethered intramolecular Diels-Alder reaction.
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