Syntheses of spiro[2,3-dihydro-4H-l-benzopyran-4,l'-cyclohexan]-2-one derivatives by reaction sequences including a radical reaction and a total synthesis of (±)-lycoramine (2) are described. Radical reactions (BuaSnH, AIBN) of 1-[(l'-cyclohexenylmethyl)oxy] -2-halobenzenes 23b-d in boiling benzene gave the corresponding spiro[2,3-dihydrobenzofuran-3,l'-cyclohexanes] 26a,b in good yields, whereas the reaction of l-(l'-cyclohexenylethoxy)-2-bromobenzene (25) under similar conditions afforded a mixture of spiro[2,3-dihydro-4H-l-benzopyran-4,l,-cyclohexane] 27 and benzoxepin 28. Furthermore, the radical reaction of ethyl 2-[(2'-bromoaryl)oxy] -1-cyclohexenylacetate 37a produced ethyl 2-spiro[2,3-dihydrobenzofuran-3,l'-cyclohexane]carboxylate 38 in good yield. Compound 38 was converted to spiro[2,3-dihydro-4ff-l-benzopyran-4,l'-cyclohexane]-2,4'-dione 40 by treatment with Sml2 and then with 3 N HC1. Spiro[2,3-dihydro-4H-l-benzopyran-4,l'-cyclohexane]-2,4'-dione 40 was transformed to (±)-lycoramine (2) in four steps and 43% overall yield.

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Various kinds of water-soluble 9-acyloxyellipticine derivatives were synthesized in a search for compounds with potent antitumor activity. Antitumor activities against several tumors in mice (P388 leukemia, colon 26, Lewis lung carcinoma and B16 melanoma) were evaluated by using intravenous administration. Many compounds exhibited good antitumor activities; in particular, the glutarate derivative (5o) showed potent antitumor activity. This compound (5o) may be converted to 9-hydroxyellipticine (2) by enzyme-catalyzed hydrolysis in the body.