A domino [2+4]/[2+3] sequential annulation reaction of MBH carbonates with N-unprotected indoles has been developed to provide various pyrroloquinoline derivatives in ≤94% yield and 20:1 dr. The reaction could be either mediated by stoichiometric PCy or catalyzed by RPO via P/P═O redox cycling in the presence of phenylsilane. This method assembles polycyclic 1,7-fused indoles in one step diastereoselectively.
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http://dx.doi.org/10.1021/acs.orglett.1c04388 | DOI Listing |
Org Lett
September 2024
College of Chemistry and Chemical Engineering, Central South University, Changsha 410083, P. R. China.
Stable and easy-to-handle sodium salts of sulfonyl oximes were first identified to proceed via visible-light-driven phophine-mediated successive deoxygenation to realize the -Markovnikov hydrothiolation of alkenes, which could serve as an odorless sulfur source. Mechanistic studies revealed that the key thiyl radical intermediate could be generated from the sulfonyl oxime anion via a phosphine-mediated fragmentation and a sequential deoxygenation process. Notably, a wide range of alkenes, including acrylamides, acrylates, vinyl ketones, vinyl sulfones, and acrylonitriles, are competent substrates for this protocol, which is highly beneficial for the construction of structurally diversified organosulfur compounds.
View Article and Find Full Text PDFNature
July 2023
Organisch-Chemisches Institut, Westfälische Wilhelms-Universität, Münster, Germany.
The chemical activation of water would allow this earth-abundant resource to be transferred into value-added compounds, and is a topic of keen interest in energy research. Here, we demonstrate water activation with a photocatalytic phosphine-mediated radical process under mild conditions. This reaction generates a metal-free PR-HO radical cation intermediate, in which both hydrogen atoms are used in the subsequent chemical transformation through sequential heterolytic (H) and homolytic (H) cleavage of the two O-H bonds.
View Article and Find Full Text PDFOrg Lett
March 2022
State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Nankai University, Tianjin 300071, China.
A domino [2+4]/[2+3] sequential annulation reaction of MBH carbonates with N-unprotected indoles has been developed to provide various pyrroloquinoline derivatives in ≤94% yield and 20:1 dr. The reaction could be either mediated by stoichiometric PCy or catalyzed by RPO via P/P═O redox cycling in the presence of phenylsilane. This method assembles polycyclic 1,7-fused indoles in one step diastereoselectively.
View Article and Find Full Text PDFChem Commun (Camb)
October 2019
Department of Chemistry, Center for Supramolecular Chemistry and Catalysis, College of Sciences & Institute for Sustainable Energy, Shanghai University, 99 Shangda Road, Shanghai 200444, P. R. China.
Phosphine-mediated cascade annulations of allenyl ketone and isocyanide have been disclosed. Two molecular allenyl ketones work as different four-carbon synthons to form two rings, respectively, and thus enables the efficient synthesis of a furan-fused eight-membered ring and a spirocycle.
View Article and Find Full Text PDFChemistry
June 2017
State Key Laboratory and Institute of Elemento-organic Chemistry, College of Chemistry, Nankai University, Tianjin, 300071, P.R. China.
A new strategy for the facile access to multi-functionalized benzofurans and 4,5-dihydrobenzofurans has been explored. The advantages of the present protocol include readily obtainable starting materials, mild and metal-free conditions, expedient and practical processes, excellent yields, and easy scale-up. The reaction demonstrated high efficiency to construct two rings in a single step.
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