Five- and six–membered cyclic α-acylvinyl anionic synthons: synthesis of α-trimethylsilyl-α,β-unsaturated cycloalkenones and their conversion into 2-(hydroxydimethylsilyl)cycloalk-2-enones through carbon–silicon bond scission

Abstract

Five-and six-membered α-trimethylsilyl-α,β-unsaturated cycloalkenones were prepared by the Wurtz-Fittig coupling reaction of the corresponding 6-bromo-1,4-dioxaspiro[4,n]cycloalk-6-enes with sodium and chlorotrimethylsilane. Upon treatment with anhydrous AlCl 3 , the compounds underwent carbon-silicon bond scission to yield a novel class of compounds: the 2-(hydroxydimethylsilyl)cycloalk-2-enones.

Synthesis, antimicrobial/radical scavenging, and in‐silico investigations of a novel class of 4‐[(4′‐hydroxymethylphenyl)‐1H‐1′,2′,3′‐triazol‐1‐yl‐methyl]‐2H‐chromen‐2‐ones

“…The plausible mechanism for the formation of products 2a-j is reasoned to go through the activation of the silyl-group of the 4-((4-trimethylsilyl-1H-1,2,3-triazol-1-yl)methyl)-2H-chromen-2-ones by TBAF to form an activated penta-coordinated silyl-intermediate, which mediates the transfer of differently substituted 4-((4-trimethylsilyl-1H-1,2,3-triazol-1-yl)methyl)-2Hchromen-2-ones nucleophile via a hexa-coordinated specie. The proposed mechanism for our products is highlighted in Scheme 2; in accordance with our earlier findings [10], and analogous to the mechanism proposed by Lettan and Scheidt [11].…”