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An efficient strategy for the construction of 3-sulfenylindoles and 3-arylindoles based on a one-pot relay Sc(III)/base-promoted Michael addition/cyclization/aromatization process has been developed. Different types of nucleophiles (thio- and carbon nucleophiles) react with -alkynyl -quinone methides (--AQMs) generated in situ from 1-(-aminophenyl)prop-2-ynols to afford the indole derivatives in moderate to excellent yields. This method displays the advantages of mild conditions, simple starting materials, and broad substrate scope.
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http://dx.doi.org/10.1021/acs.joc.5c00182 | DOI Listing |
J Org Chem
August 2025
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, Gansu 730000, P. R. China.
Pepluacetal is a structurally unique pepluanol family diterpenoid bearing an all-carbon [5-4-7-3] tetracyclic backbone. We describe herein the detailed process of the total synthesis of pepluacetal through the evolution of synthetic strategies. In the final successful strategy, a photoinduced Wolff rearrangement/lactonization cascade reaction gives access to the cyclobutane moiety; a ring-closing metathesis/cyclopropanation sequence rapidly builds up the [7-3] bicycle, and a Rh-catalyzed carbenoid insertion of the cyclobutane methylene C(sp)-H bond, followed by ring-opening manipulations, introduces the three-carbon branched side chain stereoselectively in a remote traceless stereochemical relay fashion.
View Article and Find Full Text PDFOrg Lett
June 2025
Shaanxi Key Laboratory of Natural Products & Chemical Biology, College of Chemistry and Pharmacy, Northwest A&F University, Yangling 712100, Shaanxi, P. R. China.
A relay Rh(II)/Pd(0) dual-catalyzed three-component allylic alkylation of alcohols, α-diazo 1,3-diketones, and allyl reagents is successfully developed, which provides a highly chemoselective method for the one-pot synthesis of acyclic α-quaternary allylated β-keto-esters. Remarkably, this transformation includes difunctionalizations of ketene intermediates instead of metal-carbene intermediates. Our protocol is characterized by mild conditions, simple raw materials, and good to excellent yields.
View Article and Find Full Text PDFJ Org Chem
June 2025
School of Chemical and Environmental Engineering, Shanghai Institute of Technology, 100 Haiquan Road, Shanghai 201418, PR China.
An efficient strategy for the construction of 3-sulfenylindoles and 3-arylindoles based on a one-pot relay Sc(III)/base-promoted Michael addition/cyclization/aromatization process has been developed. Different types of nucleophiles (thio- and carbon nucleophiles) react with -alkynyl -quinone methides (--AQMs) generated in situ from 1-(-aminophenyl)prop-2-ynols to afford the indole derivatives in moderate to excellent yields. This method displays the advantages of mild conditions, simple starting materials, and broad substrate scope.
View Article and Find Full Text PDFJ Am Chem Soc
May 2025
Yusuf Hamied Department of Chemistry, University of Cambridge, Cambridge CB2 1EW, United Kingdom.
The dehomologative conversion of linear or α-methyl aldehydes to vinyl boronates is achieved via a one-pot sequence of rhodium-catalyzed transfer dehydroformylation and transfer borylation of the resulting alkenes. Similarly, allylic or aliphatic alcohols are converted to vinyl boronates through a sequence involving, respectively, rhodium-catalyzed isomerization or transfer dehydrogenation to aldehyde intermediates, followed by dehydroformylation-borylation. The vinyl boronates can be further hydrogenated to alkyl boronates using the same rhodium precatalyst, enabling all five catalytic steps with a single catalyst system.
View Article and Find Full Text PDFOrg Lett
May 2025
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China.
The stereodivergent synthesis of δ-lactones, which are prevalent in natural product frameworks, from simple starting materials via a single transformation remains a significant challenge. Herein, we report an enantio- and diastereodivergent cascade reaction for the modular synthesis of chiral δ-lactones bearing two nonadjacent quaternary and tertiary carbon stereocenters. This approach employs bimetallic Ru/Cu relay catalysis between allylic alcohols and azaaryl acetates.
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