Skip to content
DraconiticResearch
Search Sources API
189,280 studies31 sourcesUpdated 29 min ago
PreprintCC BYChemRxiv

Site-Selective Radical Carbonylation of Aryl Thianthrenium Salts with Gaseous CO in Flow

  • Zhen He1,2
  • Cassandra Henderson1,2
  • Julian Quévarec1,2
  • Nikolaos Kaplaneris1,2
  • Fabian Raymenants1,2
  • Runkang Liu1,2
  • Nicola Bragato1,2,3
  • Umberto Sangalli1,2,4
  • Giulia Fiorani3
  • Timothy Noël1,2
  • Timothy Noel
4 affiliations
  1. 1Flow Chemistry Group
  2. 2Van ’t Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam
  3. 3Dipartimento di Scienze Molecolari e Nanosistemi, Universit`a Ca' Foscari Venezia, Via Torino 155, Venezia, Italy, 30172
  4. 4Dipartimento di Chimica, Università degli Studi di Pavia, Via Taramelli 12, Pavia, Italy, 27100
Open at sourcePDFDOICite

Abstract

Site-selective carbonylation of complex arenes remains challenging, particularly when carbon monoxide must intercept short-lived radical intermediates. Here, we report a photoredox carbonylation of aryl thianthrenium salts with gaseous CO and Michael acceptors in continuous flow. Pressurized gas–liquid flow facilitates the interception of photogenerated aryl radicals by CO, generating acyl radicals that subsequently engage diverse Michael acceptors to furnish 1,4-dicarbonyl derivatives. The method is compatible with a broad range of functional groups, heterocycles, pharmaceuticals, and natural-product-derived substrates, and its synthetic utility is demonstrated through a three-step synthesis of fenbufen from biphenyl and diversification of a salicin-derived 1,4-diketone into several heterocycles. This strategy combines siteselective arene thianthrenation with flow radical carbonylation, providing a versatile approach to the late-stage installation of carbonyl-containing motifs in complex molecules.

Related

  1. Enantioselective synthesis of axially chiral α-ketoamide diaryl ethers via asymmetric double carbonylation of cyclic iodonium salts
    Wang Yao, Xiao-Feng Wu
    Chemical sciencePeer-reviewedCC BYFull textOrganic chemistryEurope PMCEurope PMCPMC
  2. Copper-catalyzed radical carbonylation platform for the synthesis of N-acyl azoles under 1 bar of CO.
    Maoyi Dai, Mao-Lin Yang, Xiao-Feng Wu
    Chemical sciencePeer-reviewedCC BYFull textOrganic chemistryEurope PMC
  3. A photoinduced, FeX3-catalyzed, stereo- and regio-selective halofunctionalization of olefins with MXn via a radical-polar crossover reaction
    Jing Huang, Yidong Liu, Shen Li +7
    Communications ChemistryPeer-reviewedCC BY-NC-ND 4.0Full textOrganic chemistryCrossref
  4. Visible-light-Enabled O-Selective Radical Etherification of 1,2-Dicarbonyl Compounds for the Synthesis of Sterically Congested Ethers
    Shengkun Guo, Sita Claesen, Erik V. Van der Eycken +1
    ChemRxivPreprintCC BYFull textOrganic chemistryChemRxiv
  5. Cobalt Photocatalyzed Carbonylation Reactions in Flow: From Mass-Transfer to Light-Limited Regimes
    Mónica Martínez-Aguirre, Rowan M. Bailey, Janusz Siwek +5
    ChemRxivPreprintLicence not statedGeneral chemistryChemRxiv

Cite

BibTeXRIS
BibTeX
@misc{he2026siteselective,
  title = {{Site-Selective Radical Carbonylation of Aryl Thianthrenium Salts with Gaseous CO in Flow}},
  author = {Zhen He and Cassandra Henderson and Julian Quévarec and Nikolaos Kaplaneris and Fabian Raymenants and Runkang Liu and Nicola Bragato and Umberto Sangalli and Giulia Fiorani and Timothy Noël and Timothy Noel},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15009832/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009832/v1},
  note = {CC BY},
}
RIS
TY  - UNPB
TI  - Site-Selective Radical Carbonylation of Aryl Thianthrenium Salts with Gaseous CO in Flow
AU  - Zhen He
AU  - Cassandra Henderson
AU  - Julian Quévarec
AU  - Nikolaos Kaplaneris
AU  - Fabian Raymenants
AU  - Runkang Liu
AU  - Nicola Bragato
AU  - Umberto Sangalli
AU  - Giulia Fiorani
AU  - Timothy Noël
AU  - Timothy Noel
PY  - 2026
DA  - 2026/10/04
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15009832/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009832/v1
AB  - Site-selective carbonylation of complex arenes remains challenging, particularly when carbon monoxide must intercept short-lived radical intermediates. Here, we report a photoredox carbonylation of aryl thianthrenium salts with gaseous CO and Michael acceptors in continuous flow. Pressurized gas–liquid flow facilitates the interception of photogenerated aryl radicals by CO, generating acyl radicals that subsequently engage diverse Michael acceptors to furnish 1,4-dicarbonyl derivatives. The method is compatible with a broad range of functional groups, heterocycles, pharmaceuticals, and natural-product-derived substrates, and its synthetic utility is demonstrated through a three-step synthesis of fenbufen from biphenyl and diversification of a salicin-derived 1,4-diketone into several heterocycles. This strategy combines siteselective arene thianthrenation with flow radical carbonylation, providing a versatile approach to the late-stage installation of carbonyl-containing motifs in complex molecules.
ER  -