Modular synthesis of oligoacetylacetones via site-selective silylation of acetylacetone derivatives

Oligoacetylacetones consisting of 3,3-disubstituted pentane-2,4-diones were synthesized through a terminal silylation and oxidative coupling protocol. Highly selective formation of mono-enol silyl ethers of 3,3-disubstituted acetylacetones was achieved using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)...

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Bibliographic Details
Published in:Organic & biomolecular chemistry 2020-05, Vol.18 (17), p.3297-3302
Main Authors: Sarkar, Parantap, Inaba, Yuya, Shirakura, Hayato, Yoneda, Tomoki, Inokuma, Yasuhide
Format: Article
Language:English
Subjects:
Acetylacetone
Chemical reactions
Coupling
Crystallography
Derivatives
Ethers
Isomers
Melting points
Molecular conformation
NMR
Nuclear magnetic resonance
Pentane
Silver
Single crystals
X ray analysis
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Summary:Oligoacetylacetones consisting of 3,3-disubstituted pentane-2,4-diones were synthesized through a terminal silylation and oxidative coupling protocol. Highly selective formation of mono-enol silyl ethers of 3,3-disubstituted acetylacetones was achieved using 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a base. Subsequent silver(i) oxide mediated coupling reactions provided tetraketones. Unique substituent dependence was found for the terminal-selective silylation of tetraketones. Finally, octaketones (tetramers of acetylacetone derivatives) with three types of monomer sequences were prepared in their discrete forms. Single crystal X-ray analysis revealed that the solid-state conformations of oligoketone chains were predominantly governed by the ketone sequence rather than substituents. However, differences in the packing structures induced by alkyl substituents led to significant differences in melting points for the structural isomers of octaketones.
ISSN:1477-0520
1477-0539
DOI:10.1039/d0ob00501k