A route to 1,4-disubstituted aromatics and its application to the synthesis of the antibiotic culpin.
A method is described for converting tert-butyl benzoates or tert-butyl 1-naphthoates into derivatives having an alkyl or substituted alkyl group in a 1,4-relationship to an alkyl, aryl, alkenyl, or alkynyl group. Key steps in the sequence are (i) addition of an organometallic species to a cross-conjugated cyclohexadienone obtained by Birch alkylation of a tert-butyl benzoate or a tert-butyl 1-naphthoate, followed by allylic oxidation, and (ii) treatment with BiCl3 x H2O, which results in removal of the tert-butyl group and spontaneous decarboxylative aromatization. The method was applied to the synthesis of the antimicrobial fungal metabolite culpin.
Sunasee
Rajesh
R
Chemistry Department, University of Alberta, Edmonton, Alberta T6G 2G2, Canada.
Clive
Derrick L J
DL
D000478:Alkylation; D000900:Anti-Bacterial Agents / Q000138:chemical synthesis*; D001565:Benzoates / Q000737:chemistry; D001729:Bismuth / Q000737:chemistry; D002264:Carboxylic Acids / Q000737:chemistry; D006873:Hydroquinones / Q000138:chemical synthesis; D009281:Naphthalenes / Q000737:chemistry; D010084:Oxidation-Reduction
D000900:Anti-Bacterial Agents; D001565:Benzoates; D002264:Carboxylic Acids; D006873:Hydroquinones; D009281:Naphthalenes; C061467:culpin; C085312:1-naphthoic acid; D001729:Bismuth