Modular synthesis of oligoacetylacetones via site-selective silylation of acetylacetone derivatives. Issue 17 (15th April 2020)

• Record Type: Journal Article
• Authors: Sarkar, Parantap; Inaba, Yuya; Shirakura, Hayato; Yoneda, Tomoki; Inokuma, Yasuhide
• Is Part Of: Organic & biomolecular chemistry. Volume 18:Issue 17(2020)
• Page Start: 3297
• Page End: 3302
• Publication Date: 2020-04-15
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/d0ob00501k
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : Aliphatic oligoketones with tailored carbonyl and substituent sequences were modularly synthesized utilizing site-selective formation of enol silyl ethers. Their unique conformational preferences in solid-state were revealed by X-ray crystallography. Abstract : 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.