Nonclassical Arylative Meyer–Schuster Rearrangement through Ni-Catalyzed Inner-Sphere Acyloxy Migration
- Jaehan BaeJaehan BaeDepartment of Chemistry, Chung-Ang University, Seoul 06974, Republic of KoreaMore by Jaehan Bae
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- Wooin LeeWooin LeeDepartment of Chemistry, Chung-Ang University, Seoul 06974, Republic of KoreaMore by Wooin Lee
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- Ho Seong HwangHo Seong HwangDepartment of Chemistry, Chung-Ang University, Seoul 06974, Republic of KoreaMore by Ho Seong Hwang
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- Seoyeon KimSeoyeon KimDepartment of Chemistry, Chung-Ang University, Seoul 06974, Republic of KoreaMore by Seoyeon Kim
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- Jihee KangJihee KangDepartment of Chemistry, Chung-Ang University, Seoul 06974, Republic of KoreaMore by Jihee Kang
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- Naeem Iqbal*Naeem Iqbal*Email: [email protected]Department of Chemistry, University of York, Heslington, York YO105DD, U.K.More by Naeem Iqbal
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- Eun Jin Cho*Eun Jin Cho*Email: [email protected]Department of Chemistry, Chung-Ang University, Seoul 06974, Republic of KoreaMore by Eun Jin Cho
Abstract
A Ni(II)-catalyzed unconventional Meyer–Schuster rearrangement (MSR) is paired with cross-coupling through inner-sphere acyloxy migration. Various propargyl acetates react with aryl boronic acids, leading to the formation of a range of α-arylated enone derivatives. This transformation is enabled by the use of a P∧N-type phosphinooxazoline (PHOX) ligand, which allows the substrate to coordinate with the square planar Ni(II) center. It initiates arylnickelation of the alkyne moiety followed by intramolecular transposition of the acetate group. This nonclassical approach allows for the addition of electron-rich nucleophiles at the α-position without the need for redox additives. A series of controlled experiments including 18O isotope labeling studies and computational analysis corroborated the inner-sphere acyloxy migration.
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