Biomimetic Synthesis of Ascididemin and Derivatives

Marine pyridoacridine alkaloids and synthetic analogues as antitumor agents

“…38 Bracher used also a similar reaction scheme for the synthesis of bromoleptoclinidone, and so did Kitahara et al for both 11-hydroxyascididemin and neocalliatine acetate synthesis. 20 Two other synthesis of ascididemin also based on an addition of amine on 5,8-quinolinedione were proposed by Gellerman et al 39 and Cuerva et al, 40 respectively. The first authors described a two step biomimetic synthesis of ascididemin using N-trifluoroacetamidokynuramine as the amine in the first step.…”

“…Direct nitration of ascididemin was reported by Gellerman and Kashman to give the nitroderivatives 85 and 86. 39 For our part, we studied a series of other D-substituted analogues 87-97 43 , (Table IV). Copp and co-workers have synthesized various pyridine ring-E analogues in an attempt to determine the pharmaceutical utility and structure-activity requirement for ascididemin.…”

“…Other pentacyclic analogues of ascididemin were published involving a modified cycle. Blanco et al studied 1,2,3,4-tetrahydroascididemin 105 46 whereas both Lindsay et al 47 and Koller et al 48 were interested in the carba-analogue 106 which was obtained from adaptation of synthetic methods of ascididemin by Bracher 36 or Gellerman et al, 39 respectively. Synthesis of 105 proceeded via the acridone 107 which was readily prepared in four steps from 2-N-3,6-dimethoxyacetophenone.…”

Synthesis of Ascididemine and an Isomer

“…We present here a full description of our total synthesis of ascididemine (9H-quino[4,3,2-de] [1,10]phenanthrolin-9one (1) and of an isomer, 9H-quino[4,3,2-de] [1,7]phenanthrolin-9-one (4) in which the D ring nitrogen is at position 10 not position 13. The name ''isoascididemine'' has already been given to a synthetic, structural isomer (8Hbenzo[b]pyrido [4,3,2-de]phenanthrolin-8-one) of ascididemine.…”

“…The name ''isoascididemine'' has already been given to a synthetic, structural isomer (8Hbenzo[b]pyrido [4,3,2-de]phenanthrolin-8-one) of ascididemine. [7] There have been three previous syntheses [8][9][10] of ascididemine, each of which adopted quite different strategies from that described here.…”