Copper-Catalyzed 1,3-Propargyl Shift: Development of an Anionic Rearrangement of ortho-Metalated Aryl Propargyl Ethers
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Updated: Oct 31, 2026
![[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Azusa Kondoh1, Aderian Novito Setiawan2, Takuma Sato2
1Research and Analytical Center for Giant Molecules, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578, Japan.
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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