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Updated: Apr 13, 2026

Facile Preparation of 2Z,4E-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Ruthenium(0) Catalyzed Endiyne-α-Ketol [4 + 2] Cycloaddition: Convergent Assembly of Type II Polyketide Substructures
Aakarsh Saxena1, Felix Perez1, Michael J Krische1
1University of Texas at Austin, Department of Chemistry and Biochemistry, Austin, Texas 78712, United States.
Abstract:
Upon exposure of 3,4-benzannulated 1,5-diynes (benzo-endiynes) to α-ketols (α-hydroxyketones) in the presence of Ru(0) catalysts derived from Ru3(CO)12 and RuPhos or CyJohnPhos, successive redox-triggered C-C coupling occurs to generate products of [4 + 2] cycloaddition. The proposed catalytic mechanism involves consecutive alkyne-carbonyl oxidative couplings to form transient oxaruthanacycles that suffer α-ketol mediated transfer hydrogenolysis. This process provides a new, convergent means of assembling Type II polyketide substructures.
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