The known tetralone 5 has been regiospecifically converted in 10 steps (11% yield) to the 6-deoxy tetracyclic ketone 15. Our sequence includes a novel one-step oxidation of 2 to naphthaldehyde 6, and an unusual enone to phenol isomerization (12 * 14). Although C-7 functionalization of carbinol 17 failed, olefin 18 was converted to diol 4. The properties of 4 did not agree with those reported for y-cit"romycinone, suggesting that the latter has the"isomeric structure &. Recent advances in the regiospecific synthesis of anthracyclinones have provided several viable routes to compounds bearing the 6,11-dihydroxylated B-ring characteristic of daunomycinone (l).' No comparable methodology has been developed for synthesis of 6-deoxyanthracyclinones represented by the known a-citromycinone (2) and by the rare aglycone y-citromycinone, for which the two alternative structures 3 and 4 have been postulated.2 We describe here an unusual and completely regiospecific route to the 6-deoxy ketone 15 and subsequent _chemistry which permits a structural assignment for y-citromycinone.3 1 2 X=Y=OH ; X=H,Y=OH 4 X=OH,Y=H The key C-D bicyclic synthon 6 for our synthesis was prepared by a remarkable one-pot reaction. This transformed the known tetralone 54 by oxidation with 3.2 eqt of DDQ and 1 eqt of HC(OCHJ)B in CH30H (reflux, 24 h) directly to"naphthaldehyde 6, mp 89-90", in 65% yield.' Emmons condensation (1.2 eqt (Et0)2POCH2C02Et, 1.5 eqt NaH, C6H6, rt, 4 h)6 and subsequent hydrogenation (H2, 5% Pd-C, EtOH, rt) gave 92% of the ester 7, mp 62-64", which on Claisen acylation (1.0 eqt Et2 oxalate, 2.0 eqt NaH, C6H6, 55', 20 hj7 gave 68% of the ketodiester 8. This was reacted with methyl vinyl ketone (cat Et3N, 1:l EtOH-C6H6, reflux, 20 h) to yield 80% of the Michael adduct 9, mp 110-111". The latter was cyclized by way of the in situ gener--ated enamine (xs pyrroyidine, C H 6 6, cat AcOH, reflux, 5 h)' to yield exclusively the tricyclic ketodiester 10, mp 107-log", in 87% yield. Alkaline hydrolysis (5 eqt KOH, EtOH, reflux 24 h) gave the ketoacid 11, mp 215-217" dec, in 95% yield. __