A versatile Lewis acid-mediated cyclization strategy has been developed for selectively establishing zizaene-, allo-cedrane-, seco-kaurane-, and seco-atesane-type skeletons. The zizaene- and seco-atesane-type skeletons can be obtained in a cascade manner, which involves Diels-Alder reaction of cyclic enones with bis-silyloxy dienes and carbocyclization of yne-enolates through Lewis acid dependent 5- or 6-exo-dig modes. This cyclization strategy was also employed for the core synthesis of tashironin.
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http://dx.doi.org/10.1021/acs.orglett.7b02610 | DOI Listing |
Molecules
January 2025
Department of Chemistry, Acadia University, Wolfville, NS B4P 2R6, Canada.
A concise, transition metal-free four-step synthetic pathway has been developed for the synthesis of tetracyclic heterosteroidal compounds, 14-aza-12-oxasteroids, starting from readily available 2-naphthol analogues. After conversion of 2-naphthols to 2-naphthylamines by the Bucherer reaction, subsequent selective C-acetylation was achieved via the Sugasawa reaction and reduction of the acetyl group using borohydride, which resulted into the corresponding amino-alcohols. The naphthalene-based amino-alcohols underwent double dehydrations and double intramolecular cyclization with oxo-acids leading to one-pot formation of a C-N bond, a C-O bond and an amide bond in tandem, to generate two additional rings completing the steroidal framework.
View Article and Find Full Text PDFBiomedicines
January 2025
Department of Chemistry and Biochemistry, Augusta University, Augusta, GA 30912, USA.
Natural cyclic peptides, a diverse class of bioactive compounds, have been isolated from various natural sources and are renowned for their extensive structural variability and broad spectrum of medicinal properties. Over 40 cyclic peptides or their derivatives are currently approved as medicines, underscoring their significant therapeutic potential. These compounds are employed in diverse roles, including antibiotics, antifungals, antiparasitics, immune modulators, and anti-inflammatory agents.
View Article and Find Full Text PDFOrg Lett
January 2025
Engineering Research Center of Ministry of Education for Fine Chemicals, Shanxi University, Taiyuan 030006, P. R. of China.
Herein a novel and robust methodology to spiroimidazolidinones has been developed under a mild reaction. The reaction of (Z)-2-azido-3-phenylacrylic acids , aldehydes , amines , isocyanides , and isocyanides produced regioselectively spiroimidazolidinones in 71-88% yields via a sequential Ugi 4CR/Pd(0) catalyzed azide-isocyanide coupling/cyclization/rearrangement/hydroxylation reaction. Furthermore, the easily accessible starting materials, high bond-forming efficiency, and broad substituent tolerance make this strategy useful in synthetic and medicinal chemistry.
View Article and Find Full Text PDFBioorg Chem
January 2025
Key Laboratory of Novel Targets and Drug Study for Neural Repair of Zhejiang Province School of Medicine Hangzhou City University China; College of Pharmaceutical Sciences, Zhejiang University, Hangzhou 310058 Zhejiang Province, China. Electronic address:
Cyclization is a pivotal strategy for enhancing the drug-like characteristics of polypeptides. To develop potent and metabolically stable proteasome inhibitors, we generated a macrocyclic peptide skeleton using a straightforward and efficient cyclization strategy. Subsequent stability assessments confirmed the practicality of this approach.
View Article and Find Full Text PDFCurr Org Synth
January 2025
School of Chemistry and Chemical Engineering, Changsha University of Science and Technology, Changsha, 410114, China.
Nitrogen-containing heterocycles, such as indoles and quinolines, serve as the key scaffolds in numerous pharmaceuticals, pesticides, and natural products. The synthesis methods of nitrogen-containing heterocycles show significant scientific and industrial value. As a chemical intermediate featuring dual functional groups, cyanamide plays a crucial role in organic synthesis, directly affecting the development of new drugs and the design of new materials.
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