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Peer-reviewedCC BYJACS Au

Copper-Catalyzed 1,3-Propargyl Shift: Development of an Anionic Rearrangement of ortho-Metalated Aryl Propargyl Ethers.

  • Azusa Kondoh1
  • Aderian Novito Setiawan2
  • Takuma Sato2
  • Masahiro Terada2
  1. 1Research and Analytical Center for Giant Molecules, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578, Japan.
  2. 2Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578, Japan.
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Abstract

A novel anionic [1,3]-rearrangement of ortho-metalated aryl propargyl ethers was developed. A catalytic amount of copper-(I) salt efficiently promotes the 1,3-shift of a propargyl group from an oxygen atom to a carbon atom in an aryl magnesium species, affording phenol derivatives having a propargyl group at the ortho position, which are otherwise difficult to synthesize. The [1,3]-rearrangement proceeds in a stereoretentive manner, thus enabling chirality transfer for asymmetric syntheses of enantio-enriched propargyl compounds. DFT calculations were conducted to elucidate the mechanism of the 1,3-propargyl shift.

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Cite

BibTeXRIS
BibTeX
@article{kondoh2026coppercatalyzed,
  title = {{Copper-Catalyzed 1,3-Propargyl Shift: Development of an Anionic Rearrangement of ortho-Metalated Aryl Propargyl Ethers.}},
  author = {Azusa Kondoh and Aderian Novito Setiawan and Takuma Sato and Masahiro Terada},
  journal = {JACS Au},
  year = {2026},
  month = sep,
  doi = {10.1021/jacsau.6c01200},
  url = {https://europepmc.org/article/MED/42953197},
  note = {CC BY},
}
RIS
TY  - JOUR
TI  - Copper-Catalyzed 1,3-Propargyl Shift: Development of an Anionic Rearrangement of ortho-Metalated Aryl Propargyl Ethers.
AU  - Azusa Kondoh
AU  - Aderian Novito Setiawan
AU  - Takuma Sato
AU  - Masahiro Terada
PY  - 2026
DA  - 2026/09/19
JO  - JACS Au
DO  - 10.1021/jacsau.6c01200
UR  - https://europepmc.org/article/MED/42953197
AB  - A novel anionic [1,3]-rearrangement of ortho-metalated aryl propargyl ethers was developed. A catalytic amount of copper-(I) salt efficiently promotes the 1,3-shift of a propargyl group from an oxygen atom to a carbon atom in an aryl magnesium species, affording phenol derivatives having a propargyl group at the ortho position, which are otherwise difficult to synthesize. The [1,3]-rearrangement proceeds in a stereoretentive manner, thus enabling chirality transfer for asymmetric syntheses of enantio-enriched propargyl compounds. DFT calculations were conducted to elucidate the mechanism of the 1,3-propargyl shift.
SN  - 2691-3704
ER  -