Synthesis of 6-functionalized tricyclodecadienones using Barton's radical decarboxylation reaction. Generation of tricyclo[5.2.1.02,6]decatrienone, a norbornene annulated cyclopentadienone
Jie Zhu, Antonius J. H. Klunder and Binne Zwanenburg*
*Department of Organic Chemistry, University of Nijmegen, Toernooiveld, 6525 ED, Nijmegen, The Netherlands
J. Zhu, A. J. H. Klunder, B. Zwanenburg, Tetrahedron, 1995, 51, 5099-5116.
DOI: 10.1016/0040-4020(95)98707-O
Abstract
An effective synthesis of 6-functionalized endo-tricyclo[5.2.1.02,6]deca-4,8-dien-3-ones starting from carboxylic acid has been accomplished whereby the chemical scope of the tricyclodecadienone system as a synthetic equivalent of cyclopentadienone has been expanded.
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Details
The document details the synthesis of 6-functionalized tricyclodecadienones using Barton's radical decarboxylation reaction. The authors, Jie Zhu, Antonius J.H. Klunder, and Binne Zwanenburg, from the University of Nijmegen, describe an effective method starting from carboxylic acids. The process involves converting the acid into an acyl chloride, followed by treatment with N-hydroxypyridine-2-thione sodium salt and a radical trapping agent. This method avoids the use of molecular halogens, which can react undesirably with the norbornene moiety. The resulting 6-functionalized tricyclodecadienones can undergo further transformations, such as dehydrohalogenation to form tricyclodecatrienones, which can participate in regioselective nucleophilic additions or Diels-Alder cyclizations. The study also explores the introduction of various substituents, including halogens, sulfur, and oxygen-containing groups, demonstrating the versatility and synthetic scope of the tricyclodecadienone system. The document includes detailed experimental procedures and results, highlighting the potential applications of these compounds in the synthesis of natural products and complex cage structures.
Key Words
Barton Decarboxylation, Diels-Alder Reaction
ID: J72-Y1995-280
