Synthetic Studies on the Antitumor Benzo[c]phenanthridine Alkaloids Directing toward Medicinals Development

1)CsF存在下芳基炔丙基醚的Claisen重排反应。在CsF存在下，伯炔丙基醚的Claisen重排仅得到芳基呋喃衍生物。以β-萘酚衍生物（1）为原料，详细考察了反应条件：（a）最佳溶剂为二乙基苯胺，（B）CsF是必需的。使用化合物（2-4）研究反应的一般性。2）芳基呋喃环的断裂。研究了衍生物（5）对呋喃环的氧化断裂反应。结果表明，5经化学计量的OsO_4，NaIO_4和aq. 3）白屈菜红碱（8，R=Me，R '= H）及相关化合物的合成研究。化合物（7）在CsF存在下经Claisen重排，氧化裂解生成水杨醛衍生物，再转化为白屈菜红碱（8，R=Me，R '= H）。从抗肿瘤活性的观点出发，对酚碱（8，R=Me，R '= OH）的合成进行了研究，并以较高的收率合成了关键中间体，对包括合成中间体在内的各种化合物进行了生物活性测定。

1)Claisen Rearrangement of Aryl propargyl ether in the Presence of CsF. Claisen rearrangement of primary propargyl ether in the presence of CsF afforded exclusively the arylfuran derivated. The reaction condition was examined in detail using beta-naphtol derivatives (1) : (a)the best solvent is diethylaniline; (b)CsF is essential. A generality of the reaction was investigated using the compound(2-4).2)Cleavage of Arylfuran Ring. Oxidative cleavage of furan ring using derivative (5)was investigated. Consequently, successive treatment of 5 with a stoichiometric amount of OsO_4,NaIO_4, and aq. NaHCO_3 solution provided the desired salicylaldehyde (6) in a good yield.3)Synthetic Studies on Chelerythrine (8, R=Me, R'=H) and the related compounds. The compound (7) was prepared by two routes using Claisen rearrangement in the presence of CsF and then, oxidatively cleaved to salicylaldehyde derivatives, which was converted to chelerythrine (8, R=Me, R'=H). Synthesis of phenolic base (8, R=Me, R'=OH) was also examined from the viewpoint of antitumor activity and the key intermediate was prepared in a high yield.The biological assay of a various compounds including synthetic intermediates was under investigation.