An new approach to 2-(arylmethyl)aldehydes based upon a 1,2-anionotropic rearrangement of an aryl group is presented. The synthetic sequence begins with a silylformylation reaction of terminal acetylenes with aryl and heteroaryl silanes, followed by treatment of the products (Z)-1 with TBAF. The optimisation 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 b-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-functionalised substrates undergo an intramolecular reaction that affords exclusively carbacyclobenzyl aldehydes, further enhancing the high synthetic value of this method.
Fluoride Promoted Rearrangement of Organo Silicon Compounds: A new Synthesis of 2-(Arylmethyl)aldehydes from 1-Alkynes
2003
Abstract
An new approach to 2-(arylmethyl)aldehydes based upon a 1,2-anionotropic rearrangement of an aryl group is presented. The synthetic sequence begins with a silylformylation reaction of terminal acetylenes with aryl and heteroaryl silanes, followed by treatment of the products (Z)-1 with TBAF. The optimisation 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 b-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-functionalised substrates undergo an intramolecular reaction that affords exclusively carbacyclobenzyl aldehydes, further enhancing the high synthetic value of this method.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
