Fluoride-Promoted Rearrangement of Organo Silicon Compounds:  A New Synthesis of 2-(Arylmethyl)aldehydes from 1-Alkynes

Laura Antonella Aronica, Patrizio Raffa, Anna Maria Caporusso, and Piero Salvadori*
Dipartimento di Chimica e Chimica Industriale, Universit degli Studi di Pisa, Via Risorgimento 35, 56126 Pisa, Italy
J. Org. Chem., 2003, 68 (24), pp 9292–9298
DOI: 10.1021/jo0351062
Publication Date (Web): October 28, 2003
Copyright © 2003 American Chemical Society
*

 Corresponding author.

, psalva@dcci.unipi.it

Abstract

Abstract Image

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 β-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.

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History

  • Published In Issue November 28, 2003
  • Received July 29, 2003

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