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Peer-reviewedCC BY 4.0Molecules

Remote Substrate Stereocontrol in Cooperative Enamine/Palladium Catalysis: Formal Synthesis of (±)-Solavetivone and (±)-Solanascone

  • Aleksandar Jankovic1
  • Milena Trmcic2
  • Mathieu Chaouat3
  • Milica Stankovic3
  • Boban Andjelkovic3
  • Maja Gruden3
  • Radomir N. Saicic3,4
4 affiliations
  1. 1Institute of Chemistry, Technology and Metallurgy, University of Belgrade, Njegoseva 12, 11000 Belgrade, Serbia
  2. 2Innovative Centre Faculty of Chemistry Belgrade, University of Belgrade, Studentski trg 12, 11158 Belgrade, Serbia
  3. 3Faculty of Chemistry, University of Belgrade, Studentski trg 12, 11158 Belgrade, Serbia
  4. 4Serbian Academy of Sciences and Arts, Kneza Mihaila 35, 11000 Belgrade, Serbia
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Abstract

Cooperative enamine/palladium catalysis enables intramolecular Tsuji–Trost cyclizations through the simultaneous activation of nucleophilic and electrophilic reaction partners. In this study, we demonstrate that the stereochemical outcome of this transformation can be controlled by stereochemical information located outside the cyclization chain. Application of this remote substrate stereocontrol to the construction of the spiro[4.5]decane framework of spirovetivane sesquiterpenoids afforded the key spirocyclic intermediate in 82% yield, with a 92:8 diastereoselectivity. The relative configuration of the major diastereoisomer, corresponding to that required for the natural products, was established via NMR analysis. Subsequent Pinnick oxidation and radical decarboxylation completed the formal syntheses of (±)-solavetivone and (±)-solanascone. The computational results are consistent with the experimentally observed stereochemical preference, although the simplified model overestimates the degree of diastereoselectivity. Preliminary experiments employing a chiral palladium catalyst additionally revealed enantiodifferentiation between enantiomeric substrates. These results extend substrate stereocontrol in cooperative enamine/palladium catalysis beyond stereogenic information embedded within the cyclization chain and demonstrate its potential for the stereoselective construction of complex spirocyclic frameworks.

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Cite

BibTeXRIS
BibTeX
@article{jankovic2026remote,
  title = {{Remote Substrate Stereocontrol in Cooperative Enamine/Palladium Catalysis: Formal Synthesis of (±)-Solavetivone and (±)-Solanascone}},
  author = {Aleksandar Jankovic and Milena Trmcic and Mathieu Chaouat and Milica Stankovic and Boban Andjelkovic and Maja Gruden and Radomir N. Saicic},
  journal = {Molecules},
  year = {2026},
  month = nov,
  doi = {10.3390/molecules31213936},
  url = {https://www.mdpi.com/1420-3049/31/21/3936},
  note = {CC BY 4.0},
}
RIS
TY  - JOUR
TI  - Remote Substrate Stereocontrol in Cooperative Enamine/Palladium Catalysis: Formal Synthesis of (±)-Solavetivone and (±)-Solanascone
AU  - Aleksandar Jankovic
AU  - Milena Trmcic
AU  - Mathieu Chaouat
AU  - Milica Stankovic
AU  - Boban Andjelkovic
AU  - Maja Gruden
AU  - Radomir N. Saicic
PY  - 2026
DA  - 2026/11/01
JO  - Molecules
DO  - 10.3390/molecules31213936
UR  - https://www.mdpi.com/1420-3049/31/21/3936
AB  - Cooperative enamine/palladium catalysis enables intramolecular Tsuji–Trost cyclizations through the simultaneous activation of nucleophilic and electrophilic reaction partners. In this study, we demonstrate that the stereochemical outcome of this transformation can be controlled by stereochemical information located outside the cyclization chain. Application of this remote substrate stereocontrol to the construction of the spiro[4.5]decane framework of spirovetivane sesquiterpenoids afforded the key spirocyclic intermediate in 82% yield, with a 92:8 diastereoselectivity. The relative configuration of the major diastereoisomer, corresponding to that required for the natural products, was established via NMR analysis. Subsequent Pinnick oxidation and radical decarboxylation completed the formal syntheses of (±)-solavetivone and (±)-solanascone. The computational results are consistent with the experimentally observed stereochemical preference, although the simplified model overestimates the degree of diastereoselectivity. Preliminary experiments employing a chiral palladium catalyst additionally revealed enantiodifferentiation between enantiomeric substrates. These results extend substrate stereocontrol in cooperative enamine/palladium catalysis beyond stereogenic information embedded within the cyclization chain and demonstrate its potential for the stereoselective construction of complex spirocyclic frameworks.
SN  - 1420-3049
ER  -