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J Org Chem. 2004 Dec 10;69(25):8731-8.

Electrochemical synthesis of dimerizing and nondimerizing orthoquinone monoketals.

Author information

1
Laboratoire de Chimie des Substances Végétales, Centre de Recherche en Chimie Moléculaire, Université Bordeaux 1, 351 cours de la Libération, F-33405 Talence Cedex, France.

Abstract

Anodic oxidation of appropriately substituted 2-methoxyphenols or alpha-(2-methoxyphenoxy)-2-methylpropionic acids in the presence of methanol furnishes stable orthoquinone monoketals, and thus constitutes a valuable alternative to the use of chemical oxidants that are often based on toxic metallic species. The propionic acid derivatives are initially converted into O-spirolactonic quinone bisketals that are then selectively hydrolyzed into the desired monoketal compounds. In the absence of blocking substituents, orthoquinone monoketals spontaneously undergo Diels-Alder dimerizations into tricyclododecadienedienones with extraordinary site selectivity, regioselectivity, and stereoselectivity. Suggestions are made to open up a new track for a long awaited rationalization of these controls on the basis of the intramolecular [2 + 2] reactivity of these orthoquinone monoketal-derived cyclodimers.

PMID:
15575750
DOI:
10.1021/jo048677i
[Indexed for MEDLINE]

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