Bicyclo[m.n.1]alkenone frameworks possessing quaternary carbon centers adjacent to a bridged ketone are frequently found in bioactive natural products. Although several methods have been developed to construct such frameworks, most of them are specific to a particular scaffold. Herein, we report a mild and highly efficient method to generate carbon-bridged frameworks of various sizes using phosphino gold(I) catalysts.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/ol901722q | DOI Listing |
ACS Omega
December 2024
Laboratoire de Chimie Organique, Service de Chimie et PhysicoChimie Organiques, Université libre de Bruxelles (ULB), Avenue F. D. Roosevelt 50, CP160/06, Brussels 1050, Belgium.
An in-depth experimental and computational study to rationalize the mechanism underlying the gold-catalyzed intramolecular hydroalkylation of ynamides to indenes is reported. Evaluating the reactivity of a set of deuterated ynamides and gold complexes allowed to get valuable insights into the mechanism of this reaction, while DFT calculations allowed to determine a plausible reaction pathway for this unprecedented transformation. This pathway involves the activation of the ynamide followed by a [1,5]-hydride shift from the highly reactive, in situ generated keteniminium ion, and a subsequent cyclization before deprotonation followed by a final protodeauration.
View Article and Find Full Text PDFNat Commun
December 2024
Shaanxi Key Laboratory of Natural Products & Chemical Biology, College of Chemistry & Pharmacy, Northwest A&F University, Yangling, Shaanxi, 712100, China.
Marine cyclopianes are a family of diterpenoid with novel carbon skeleton and diverse biological activities. Herein, we report our synthetic and chemical proteomics studies of cyclopiane diterpenes which culminate in the asymmetric total synthesis of conidiogenones C, K and 12β-hydroxy conidiogenone C, and identification of Immunity-related GTPase family M protein 1 (IRGM1) as a cellular target. Our asymmetric synthesis commences from Wieland-Miescher ketone and features a sequential intramolecular Pauson-Khand reaction and gold-catalyzed Nazarov cyclization to rapidly construct the 6-5-5-5 tetracyclic skeleton.
View Article and Find Full Text PDFJ Org Chem
December 2024
School of Materials Science & Engineering, Beijing Institute of Technology, Beijing 100081, China.
A gold-catalyzed sulfonylation of aryl/vinyl iodides to synthesize aryl sulfones facilitated by the ligand-enabled Au(I)/Au(III) redox catalysis was developed. In the reaction, aryl sodium sulfinates or sulphinic acids can react smoothly with aryl/vinyl iodides to directly construct various aryl sulfones. The strong synthetic capabilities of sulfone synthesis are demonstrated by its easily available and handled reagents, good functional group compatibility, and late-stage application of complicated biomolecules.
View Article and Find Full Text PDFJ Org Chem
December 2024
College of Chemistry and Chemical Engineering, Shaanxi University of Science and Technology, Xi'an 710021, P. R. China.
J Am Chem Soc
December 2024
Department of Applied Chemistry for Environment, Graduate School of Urban Environmental Sciences, Tokyo Metropolitan University, 1-1 minami-Osawa, Hachioji 192-0397, Tokyo, Japan.
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!