In situ formation of heterobimetallic Pt-Ti catalysts enables rapid room temperature catalysis in enyne cycloisomerization reactions. The Lewis acidic titanium atom in the ligand framework is shown to be essential for fast catalysis. A range of enyne substrates are efficiently cyclized to carbocycles and heterocycles in high yield.
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http://dx.doi.org/10.1039/c6dt01783e | DOI Listing |
Org Lett
December 2024
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Science, Zhejiang Normal University, 688 Yingbin Road, Jinhua 321004, China.
An unexpected cascade reaction of enyne-amides with sulfur-ylides has been developed. This cascade reaction involves cycloisomerization, dearomatic cyclopropanation, ring-opening rearomatization, and subsequent cyclopropanation, differing from the common [2 + n] cyclization of enyne-amides. A variety of (spirocyclopropane)dihydrofuran derivatives have been efficiently and conveniently synthesized in a single vessel, exhibiting excellent diastereoselectivity and good functional group tolerance.
View Article and Find Full Text PDFOrg Lett
November 2024
Department of Chemistry, Institute of Science, Banaras Hindu University, Varanasi 221005, India.
Enyne diesters derived from 2-propargyloxyarylaldehydes are converted into 2-oxopyranochromenes via In(OTf)-catalyzed cycloisomerization and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)-mediated oxidative cyclization reaction sequence in one pot. The process possesses broad substrate scope and good functional group compatibility and generates various 4-(hetero)aryl-substituted 2-oxopyranochromenes in 32-79% yields (over two steps). 2-Oxopyranochromenes undergo selective decarboxylation under Krapcho conditions.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
Department of Chemistry and Biochemistry, University of California Santa Barbara, Santa Barbara, CA 93117, USA.
Cyclopentene rings possessing a chiral quaternary center are important structural motifs found in various natural products. In this work, we disclose expedient and efficient access to this class of synthetically valuable structures via highly enantioselective desymmetrization of prochiral propargylic alcohols. The efficient chirality induction in this asymmetric gold catalysis is achieved via two-point bindings between a gold catalyst featuring a bifunctional phosphine ligand and the substrate homopropargylic alcohol moiety-an H-bonding interaction between the substrate HO group and a ligand phosphine oxide moiety and the gold-alkyne complexation.
View Article and Find Full Text PDFOrg Lett
July 2024
Collège de France, Université PSL, Institut Parisien de Chimie Moléculaire, Sorbonne Université, CNRS, 4 place Jussieu, 75005 Paris, France.
Enantioconvergent transformations from racemic mixtures are attractive since they allow the generation of optically active products with full conversion despite the possibly adverse kinetic resolution process. When dealing with gold(I)-catalyzed cycloisomerizations, chirality transfer from the precursor is another possible diverting pathway, which renders enantioconvergence challenging. Not surprisingly, enantioconvergent Au(I)-catalyzed processes have remained extremely rare.
View Article and Find Full Text PDFJ Am Chem Soc
July 2024
Department of Chemistry and Biochemistry, The Ohio State University, Columbus, Ohio 43210, United States.
Herein, we report room temperature, atom-economic protocols for high regio- and enantioselective tandem cycloisomerization-hydroarylation and cycloisomerization-hydroalkenylation of 1,6-enynes leading to vicinal -functionalized pyrrolidines, tetrahydrofurans, and cyclopentanes. The latter steps in these processes involve carbonyl-coordination-assisted C-H activation of aromatic aldehydes and esters, and, a similar, yet rarely seen, β-C-H activation in the case of the acrylates. Synthetically useful enantioselective versions of such reactions are rare and are limited to the C-H activation of indoles and pyrroles.
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