Fluoride-promoted rearrangement of organo silicon compounds: A new synthesis of 2-(arylmethyl)aldehydes from 1-alkynes

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

*Corresponding author for this work

Research output: Contribution to journalArticleAcademicpeer-review

24 Citations (Scopus)

Abstract

A new approach to 2-(arylmethyl)aldehydes 4 based upon a 1,2-anionotropic rearrangement of an aryl group is presented. The synthetic sequence begins with a silylformylation reaction of terminal acetylenes 5 with aryl and heteroaryl silanes 6, followed by treatment of the products (Z)-1 with TBAF. The optimization of the experimental conditions of the fluoride-promoted step is described, together with the synthetic potentialities of the process. A plausible mechanism of the rearrangement reaction is reported that suggests the addition of the fluoride ion to the arylsilicon moiety of beta-silylalkenals (Z)-1 and the consequent migration of the aryl group to the adjacent carbon atom. Both aryl and heteroaryl substituents can rearrange without any loss of configuration. Bromo-functionalized substrates undergo an intramolecular reaction that affords exclusively carbacyclobenzyl aldehydes, further enhancing the high synthetic value of this method.

Original languageEnglish
Pages (from-to)9292-9298
Number of pages7
JournalJournal of Organic Chemistry
Volume68
Issue number24
DOIs
Publication statusPublished - 28-Nov-2003

Keywords

  • ALPHA-SUBSTITUTED ALDEHYDES
  • RHODIUM-CATALYZED SILYLFORMYLATION
  • PRACTICAL CHIRAL AUXILIARY
  • STEREOSELECTIVE SYNTHESIS
  • PYRROLIZIDINE ALKALOIDS
  • ORGANOSILICON COMPOUNDS
  • ASYMMETRIC-SYNTHESIS
  • TERMINAL ALKYNES
  • METAL-COMPLEXES
  • ACYL SILANES

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