A metal-controlled divergent protocol for the synthesis of α- and β-substituted γ-butyrolactones was developed through intramolecular coupling of epoxides with alcohols. This method provides an efficient and practicable way to afford γ-butyrolactones with good efficiency, excellent regioselectivity, and broad substrate scope.
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http://dx.doi.org/10.1021/acs.orglett.3c00898 | DOI Listing |
Acc Chem Res
January 2025
Department of Chemistry and Chemistry Institution for Functional Materials, Pusan National University, Busan 46241, Republic of Korea.
ConspectusControlling selectivity through manipulation of reaction intermediates remains one of the most enduring challenges in organic chemistry, providing novel solutions for selective C-C π-bond functionalization. This approach, guided by activation principles, provides an effective method for selective functional group installation, enabling direct synthesis of organic molecules that are inaccessible through conventional pathways. In particular, the selective functionalization of N-conjugated allenes and alkynes has emerged as a promising research focus, driven by advances in controlling reactive intermediates and activation strategies.
View Article and Find Full Text PDFBeilstein J Org Chem
December 2024
Department of Chemistry, Faculty of Science, Bilkent University, Ankara 06800, Türkiye.
Acenaphthylene-fused heteroarenes with a variety of five- and six-membered heterocycles such as thiophene, furan, benzofuran, pyrazole, pyridine and pyrimidine were synthesized via an efficient Pd-catalyzed reaction cascade in good to high yields (45-90%). This cascade involves an initial Suzuki-Miyaura cross-coupling reaction between 1,8-dihalonaphthalenes and heteroarylboronic acids or esters, followed by an intramolecular C-H arylation under the same conditions to yield the final heterocyclic fluoranthene analogues. The method was further employed to access polyoxygenated benzo[]fluoranthenes, which are all structurally relevant to benzo[]fluoranthene-based fungal natural products.
View Article and Find Full Text PDFChemistry
December 2024
Eotvos Lorand University, Organic Chemistry, Pazmany Peter Setany 1/A, 1117, Budapest, HUNGARY.
The present study reveals an unexpected anomaly observed in the acid-catalyzed hydrolysis of the 5,6-O-isopropylidene group in 3-O-protected D-gluco- and D-allofuranose derivatives. Although the removal of the 5,6-O-isopropylidene protecting group is typically rapid and quantitative under acidic conditions, an unexpected inhibition of this reaction is observed for the two C3-epimers, 3-O-imidazole sulfonyl moiety. X-ray data show a two-faced imidazole ring orientation in the crystal, while solution state NOE data reveal a critical interaction type between the isopropylidene and the imidazole rings.
View Article and Find Full Text PDFOrg Lett
December 2024
Eisai Inc. G2D2, 35 Cambridgepark Drive, Cambridge, Massachusetts 02140, United States.
An entirely chromium-free synthesis of eribulin, a fully synthetic macrocyclic ketone analogue of the marine natural product halichondrin B, was achieved through iterative sulfone fragment couplings followed by an intramolecular Prins reaction involving a C.26 homoallenyl alcohol and a C.27 aldehyde acetal.
View Article and Find Full Text PDFOrg Lett
December 2024
Division of Medicinal Chemistry, CSIR-Institute of Microbial Technology, Chandigarh 160036, India.
A novel palladium-catalyzed intramolecular C-H amination via oxidative coupling exploiting inactivated N-substituted aryl amines on indoles for the one-pot synthesis of novel 11-benzo[4,5]imidazo[1,2-]indole derivatives is reported. The optimized reaction conditions accommodated a wide range of electronic variations on both the indole and the pendant aryl amine ring, resulting in products with good to excellent yields.
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