Silylformylation - Fluoride-assisted aryl migration of acetylenic derivatives in a versatile approach to the synthesis of polyfunctionalised compounds

LA Aronica*, P Raffa, G Valentini, AM Caporusso, P Salvadori

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

10 Citations (Scopus)

Abstract

Polyfunctionalised aldehydes and dihydropyrans are prepared from easily available functionalised 1-alkynes through a two-step silylformylation/aryl migration sequence. The silylformylation process is performed under mild experimental conditions and affords the corresponding beta-silylalkenals in high yields. The fluoride-promoted migration step occurs instantaneously with quantitative conversion. The chemo-, regio- and stereoselectivity can be modulated according to the nature and the position of the functional group on the acetylene precursors. When a good leaving group is present in the omega position of the aliphatic chain of the alkyne a cyclisation product is obtained, while a,p-unsaturated aldehydes are generated from propargylic tosylamides. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006).

Original languageEnglish
Pages (from-to)1845-1851
Number of pages7
JournalEuropean Journal of Organic Chemistry
Issue number8
DOIs
Publication statusPublished - 10-Apr-2006

Keywords

  • alkynes
  • carbonylation
  • rearrangement
  • aldehydes
  • OXYNITRILASE-CATALYZED TRANSFORMATION
  • TERMINAL ALKYNES
  • SUBSTITUTED ALDEHYDES
  • METAL-COMPLEXES
  • SILICON
  • 1-ALKYNES
  • REARRANGEMENT
  • CYCLIZATION
  • ESTERS
  • BONDS

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