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PreprintCC BY-NC-NDChemRxiv

Diverse Remote Difunctionalization of Enyne-type Propargylic Carbonates: Regio-, Chemo-, and Stereoselective Access to Highly Functionalized Multisubstituted 1,3-Dienes

  • Shan Wang1,2,3,4
  • Ming Jiang1,2
  • Yifei Zheng1,2
  • Gengchen Li1,2
  • Yubin Lin1,2
  • Long Li1,2
  • Haoming Cheng3,4
  • Xiaoguang Li3,4
  • Zheng Wang3,4
  • Yingcheng Wang1,2
  • Fangzhi Peng1,2
  • Zhihui Shao1,2,5
1 more authors
  • long li
5 affiliations
  1. 1Key Laboratory of Medicinal Chemistry for Natural Resource, Ministry of Education, School of Chemical Science and Technology, and State Key Laboratory for Conservation and Utilization of Bio-Resources in Yunnan
  2. 2Yunnan University
  3. 3School of Artificial Intelligence
  4. 4Shenzhen University
  5. 5Southwest United Graduate School
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Abstract

Herein, we report the first catalytic heterodifunctionalization and homodifunctionalization of readily available 1-substituted enyne-type propargylic derivatives, proceeding via a multicomponent remote C2,C5-addition/substitution pathway. This palladium-catalyzed protocol enables the modular and straightforward assembly of tri-, tetra-, and penta-substituted 1,3-dienes with diverse functional groups from two heteroatom nucleophiles or one heteroatom nucleophile and one carbon nucleophile. The reaction exhibits high chemo-, regio-, and stereoselectivity, accommodates a broad spectrum of O-, N-, S-, and C-nucleophiles, and delivers highly substituted (Z, E)-1,3-dienes with precise stereocontrol. Notably, switching from O- to S-nucleophiles triggers a nucleophile-directed stereodivergence. The synthetic utility is further demonstrated through diverse downstream transformations, efficient synthesis of bioactive molecules, and late-stage functionalization of natural products. Mechanistic studies reveal the involvement of heteroatom-containing pentacoordinate π-allyl palladium and π-alkynyl palladium intermediates in this heterodifunctionalization process.

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Cite

BibTeXRIS
BibTeX
@misc{wang2026diverse,
  title = {{Diverse Remote Difunctionalization of Enyne-type Propargylic Carbonates: Regio-, Chemo-, and Stereoselective Access to Highly Functionalized Multisubstituted 1,3-Dienes}},
  author = {Shan Wang and Ming Jiang and Yifei Zheng and Gengchen Li and Yubin Lin and Long Li and Haoming Cheng and Xiaoguang Li and Zheng Wang and Yingcheng Wang and Fangzhi Peng and Zhihui Shao and long li},
  howpublished = {ChemRxiv},
  year = {2026},
  month = oct,
  doi = {10.26434/chemrxiv.15010221/v1},
  url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010221/v1},
  note = {CC BY-NC-ND},
}
RIS
TY  - UNPB
TI  - Diverse Remote Difunctionalization of Enyne-type Propargylic Carbonates: Regio-, Chemo-, and Stereoselective Access to Highly Functionalized Multisubstituted 1,3-Dienes
AU  - Shan Wang
AU  - Ming Jiang
AU  - Yifei Zheng
AU  - Gengchen Li
AU  - Yubin Lin
AU  - Long Li
AU  - Haoming Cheng
AU  - Xiaoguang Li
AU  - Zheng Wang
AU  - Yingcheng Wang
AU  - Fangzhi Peng
AU  - Zhihui Shao
AU  - long li
PY  - 2026
DA  - 2026/10/11
PB  - ChemRxiv
DO  - 10.26434/chemrxiv.15010221/v1
UR  - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010221/v1
AB  - Herein, we report the first catalytic heterodifunctionalization and homodifunctionalization of readily available 1-substituted enyne-type propargylic derivatives, proceeding via a multicomponent remote C2,C5-addition/substitution pathway. This palladium-catalyzed protocol enables the modular and straightforward assembly of tri-, tetra-, and penta-substituted 1,3-dienes with diverse functional groups from two heteroatom nucleophiles or one heteroatom nucleophile and one carbon nucleophile. The reaction exhibits high chemo-, regio-, and stereoselectivity, accommodates a broad spectrum of O-, N-, S-, and C-nucleophiles, and delivers highly substituted (Z, E)-1,3-dienes with precise stereocontrol. Notably, switching from O- to S-nucleophiles triggers a nucleophile-directed stereodivergence. The synthetic utility is further demonstrated through diverse downstream transformations, efficient synthesis of bioactive molecules, and late-stage functionalization of natural products. Mechanistic studies reveal the involvement of heteroatom-containing pentacoordinate π-allyl palladium and π-alkynyl palladium intermediates in this heterodifunctionalization process.
ER  -