Direct Synthesis of 1,3-Dien-2-yl Esters from α-Allenols and Carboranyl Carboxylic Acids

-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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Publication Details

Journal
The Journal of Organic Chemistry
Published
2026-05-17
DOI
https://doi.org/10.1021/acs.joc.6c00340
Primary Topic
Boron Compounds in Chemistry
Type
article
Field-Weighted Citation Impact
0.00

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article

Direct Synthesis of 1,3-Dien-2-yl Esters from α-Allenols and Carboranyl Carboxylic Acids

Phil Ho Lee, Tae Hyeon Kim, Euijae Lee, Koustav Pal
The Journal of Organic Chemistry
Boron Compounds in Chemistry
article

Direct Synthesis of 1,3-Dien-2-yl Esters from α-Allenols and Carboranyl Carboxylic Acids

Phil Ho Lee, Tae Hyeon Kim, Euijae Lee, Koustav Pal
article en

Abstract

-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.

The Journal of Organic Chemistry
Kangwon National University (KR)
National Research Foundation of Korea
Openalex Percentile: Top 5%
Boron Compounds in Chemistry
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