Synthesis of 4,4-Dimethyl-1,6-heptadiyne and Other Neopentylene-Tethered (NPT) 1,6-Diynes.
J Org Chem
; 87(9): 5773-5784, 2022 May 06.
Article
em En
| MEDLINE
| ID: mdl-35427143
ABSTRACT
Two divergent and complementary methodologies for preparing neopentylene-tethered (NPT) 1,6-diynes are described. These NPT 1,6-diynes are valuable π-systems for reaction discovery and building blocks for target-oriented synthesis. Ring-opening fragmentation of dimedone (and alkylation) produces alkyne-tethered ß-keto esters 6. One-pot dehydration with optional saponification produces diyne monoester 15 or monoacid 3, which can be further functionalized using traditional alkyne substitution chemistry and/or carboxylate manipulations. For example, copper-catalyzed decarboxylation of acid 3 provides 4,4-dimethyl-1,6-heptadiyne (1), now in ca. 76% yield over four steps from dimedone. A complementary approach using Zard fragmentation chemistry converts alkylated ß-keto esters into the corresponding monoalkylated NPT 1,6-diynes. The utility of substituted NPT 1,6-diynes in target-oriented synthesis is noted herein.
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Base de dados:
MEDLINE
Idioma:
En
Revista:
J Org Chem
Ano de publicação:
2022
Tipo de documento:
Article
País de afiliação:
Estados Unidos