REACTION OF BENZOCYCLOBUTENOXIDES WITH ALDEHYDES - SYNTHESIS OF PESHAWARINE AND OTHER 3,4-DIHYDROISOCOUMARINS

被引:47
作者
FITZGERALD, JJ [1 ]
PAGANO, AR [1 ]
SAKODA, VM [1 ]
OLOFSON, RA [1 ]
机构
[1] PENN STATE UNIV, DEPT CHEM, UNIVERSITY PK, PA 16802 USA
关键词
D O I
10.1021/jo00094a022
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
Deprotonation of benzocyclobutenols 6 in the presence of aromatic aldehydes affords benzopyranols 7 in high yield. In the key step of this process, an o-tolualdehyde anion generated by the known ring-opening of benzocyclobutenoxides adds to the aldehyde to give 7 which is easily oxidized to 3-substituted 3,4-dihydroisocoumarins 8 including intermediates in some natural product syntheses. For example, reaction of 6-methoxybenzocyclobutenol (1) with LTMP and p-anisaldehyde gave in 96% yield the benzopyranol 16, which subsequently was converted to (+/-)-hydrangenol (17). Similar treatment of 1 with LDA and isovanillin benzyl ether afforded the benzopyranol 19 (87% yield) which already has been converted to (+/-)-phyllodulcin (21). Finally, reaction of 5,6-(methylenedioxy)-benzocyclobutenol (10) with LTMP and the aldehyde 26 (from treatment of hydrastinine with ClCO2-Me) followed by methanolysis produced the acetal 28 in 96% yield. The overall yield was 65% for the five-step synthesis of the alkaloid (+/-)-peshawawine (24) from 10 and 26. Extension of the process to aliphatic aldehydes was illustrated by the preparation of 32 from benzocyclobutenol and isobutyraldehyde in 69% overall yield after oxidation with PCC.
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页码:4117 / 4121
页数:5
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