An efficient protocol for the highly regioselective opening of aliphatic zirconacyclopentadienes is reported. The one-pot process involves a zirconocene-mediated cyclization of 1,6-diynes and highly selective cleavage of the metallacycles with NBS and enables a concise synthesis of the tetrahydrofuran-core of the leupyrrins.
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http://dx.doi.org/10.1039/c2cc37678d | DOI Listing |
J Org Chem
January 2025
Antibiotics Research and Re-evaluation Key Laboratory of Sichuan Province, Sichuan Industrial Institute of Antibiotics, School of Pharmacy, Chengdu University, 2025 Chengluo Avenue, Chengdu 610016, P.R. China.
Herein, we report the first example that P(O)-H species including -phosphonates and -phosphine oxides could participate in a highly regioselective 1,4-addition to in situ generated 1-benzopyrylium ion from C3-substituted 2-chromene hemiketals, which provides a brand-new and effective approach for the synthesis of C4-phosphorylated 4-chromenes with diverse C3-functionality (ketone, ester, sulfonyl, aryl, and alkyl groups). In total, the reaction features the use of inexpensive Zn(ClO)·6HO as a catalyst, low catalyst loading (only 5 mol %), mild reaction conditions (60 °C, 10 min to 24 h), and broad substrate scope (46 examples) as well as good to high yields (>90% yield on average). More importantly, mechanistic experiments demonstrated the essential role of the C3-substituent on 2-chromene hemiketals in stabilizing the in situ generated 1-benzopyrylium ion and the regioselective 1,4-addition control.
View Article and Find Full Text PDFJ Org Chem
January 2025
Antibiotics Research and Re-evaluation Key Laboratory of Sichuan Province, Sichuan Industrial Institute of Antibiotics, School of Pharmacy, Chengdu University, 2025 Chengluo Avenue, Chengdu 610016, P. R. China.
We report a highly regioselective 1,2-addition of P(O)-H compounds to the in situ generated β,γ-alkynyl-α-ketimine derived from 3-alkynyl-3-hydroxyisoindolinones, which provided a general protocol for the preparation of 3,3-disubstituted isoindolinones featuring both phosphoryl and alkynyl groups at a quaternary carbon center. The use of only 2-5 mol % of an inexpensive catalyst (In(ClO)·8HO or Bi(OTf)) allowed the smooth output of the desired products under mild conditions (25 °C, 0.5-24 h) with a broad substrate scope (35 examples) in up to >99% yield.
View Article and Find Full Text PDFChem Commun (Camb)
January 2025
Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, Stockholm, SE-10691, Sweden.
Herein, we present a highly efficient allylic substitution of carbonates with Grignard reagents using a reusable cellulose-supported nanocopper catalyst. This approach highlights the first instance of heterogeneous catalysis for the cross-coupling of allylic alcohol substrates with Grignard reagents. The method features high yields, excellent regioselectivity, and complete chirality transfer.
View Article and Find Full Text PDFAcc Chem Res
January 2025
Department of Chemistry, University of Wisconsin, 1101 University Avenue, Madison, Wisconsin 53706, United States.
ConspectusThe manipulation of strained rings is a powerful strategy for accessing the valuable chemical frameworks present in natural products and active pharmaceutical ingredients. Aziridines, the smallest N-containing heterocycles, have long served as building blocks for constructing more complex amine-containing scaffolds. Traditionally, the reactivity of typical aziridines has been focused on ring-opening by nucleophiles or the formation of 1,3-dipoles.
View Article and Find Full Text PDFChem Asian J
January 2025
Xiamen University, Department of Chemistry, Xiamen University, Lujiaxi Building Room 742, 361005, xiamen, CHINA.
The direct construction of polycyclic arenes through ring formation using simple building blocks is highly appealing but remains challenging in organic chemistry. In this study, we introduce an efficient cascade reaction that combines dearomatizing photocyclization with oxidative aromatization, driven by organophotocatalysis. Conducted under mild, transition-metal-free conditions, this reaction seamlessly converts styrene derivatives into a diverse array of functionalized polycyclic aromatic compounds with good yields and regioselectivity.
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