- AN EFFICIENT, REGIOSPECIFIC SYNTHESIS OF (+/-)-DAUNOMYCINONE
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The development of a general strategy for the control of regiochemistry in the Diels-Alder reactions of substituted naphthazarins is described.Application of this strategy to the synthesis of (+/-)-daunomycinone (2) employs two successive regiochemically controlled Diels-Alder reactions and leads to a ten-step, regiospecific synthesis of (+/-)-2 in 36percent overall yield (Scheme 4).
- Kelly, T. Ross,Ananthasubramanian, L.,Borah, Kripinath,Gillard, John W.,Goerner, Richard N.,et al.
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p. 4569 - 4578
(2007/10/02)
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- Synthesis of adriamycin and 7,9-epiadriamycin
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A process for the synthesis of adriamycin and 7,9-epiadriamycin, both active antineoplastic agents, in which 7-deoxydaunomycinone, in either the 9s or racemic (±) form, is employed as the starting material, the process in one embodiment also being productive of the useful intermediate compound 4-methoxy-6,11-dihydroxy-7,8-dihydro-5,9(10H),12-naphthacenetrione. The process involves converting 7-deoxydaunomicinone successively to daunomycinone, adriamycinone, 14-0-p-anisyldiphenylmethyladriamycinone and finally to adriamycin or to both adriamycin and 7,9-epiadriamycin. When producing the latter mixture of diastereomers, the 7-deoxydaunomycinone starting material is first converted to racemate form by a process involving the successive production of 7-deoxydaunorubicinol, 4-methoxy-6,11-dihydroxy-7,8-dihydro-5,9(10H), 12-naphthacenetrione, (±)-4-methoxy-9-cyano-6,9,11-trihydroxy-7,8,9,10-tetrahydro-5,12-naphthacenedione, (±)-4-methoxy-9-cyano-9-(2'-tetrahydropyranyloxy)-6,11-dihydroxy-7,8,9,10-tetrahydro-5,12-naphthacenedione and (±)-7-deoxydaunomycinone.
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