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Facile Preparation of (2Z,4E)-Dienamides by the Olefination of Electron-deficient Alkenes with Allyl Acetate
Published on: June 21, 2017
Direct Synthesis of 1,3-Dien-2-yl Esters from α-Allenols and Carboranyl Carboxylic Acids
Tae Hyeon Kim1, Koustav Pal1, Euijae Lee1
1Department of Chemistry, Kangwon National University, Chuncheon 24341, Republic of Korea.
Abstract:
We report a metal- and base-free intermolecular O-1,3-dien-2-ylation of C-carboxylated carboranes with α-allenols, enabling direct access to carborane-containing 1,3-dien-2-yl esters under mild conditions. This operationally simple protocol proceeds via dehydration of a protonated α-allenol to generate a putative α-allenyl carbocation, which is efficiently intercepted by the corresponding carboranyl carboxylate. The synthetic utility of the resulting dienyl esters is demonstrated through Diels-Alder reactions with representative dienophiles. Mechanistic investigations support the unique reactivity of carboranyl carboxylic acids and a pathway distinct from transition-metal-catalyzed intramolecular acyloxy migration manifolds.
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