Tetrahedron p. 10569 - 10582 (1996)
Update date:2022-08-04
Topics:
Rigby, James H.
Mateo, Mary E.
The total syntheses of (±)-α-lycorane and dehydroanhydrolycorine are described. The key intermediate in both approaches is the hydroindolone 5, prepared from the [1 + 4] cycloaddition reaction of 1-isocyanatocyclohexene and cyclohexyl isocyanide. Alkylation of 5 with arylbromide 6 afforded 7. Hydrolysis of enamide 7 followed by reduction of the resultant enol yielded 10 as a single diastereomer. Radical-based cyclization of this intermediate gave 11 possessing the requisite trans-fusion between rings B and C in good yield. Radical deoxygenation followed by reduction of the amide carbonyl function afforded (±)-α-lycorane. Similarly, alkylation of 5 with 6-(chloromethyl)-5-iodo-1,3-benzodioxole gave 14. Treatment of 14 with Pd(OAc)2 employing the Jeffery modification of the Heck reaction gave tetracycle 9. Hydrolysis of 9 followed by oxidation with DDQ afforded 15. Reduction of the two carbonyl functions in this material using lithium aluminum hydride afforded 4-hydroxyanhydrolycorine (16). Mesylation of the hydroxyl group led to rapid, spontaneous elimination producing anhydrodehydrolycorine.
View MoreContact:86-575-86132822,86-575-86085355
Address:No.418 Dadao West Road,Qixing Street,Xinchang, Zhejiang Province, China.
Wuhan Sunrise Pharmaceutical Technology Co., Ltd
Contact:+86-27-83314682
Address:Room 340, New material Industrial base No.17, Gu Tian Five Lu , Qiaokou District, Wuhan , China
JIANGSU GRAND XINYI PHARMACEUTICAL CO.,LTD
website:http://www.xypharm.com/
Contact:+86-515-84383317
Address:Chenli Road,Costal Chemical Area Binhai,Yancheng, Jiangsu,China
taicang liyuan chemical co,.ltd
website:http://www.tcliyuanchem.com/productse.php
Contact:86-512-53539583
Address:Room 804,Huaxu Building,No.95,Renmin South Road,Taicang city,Jiangsu Province,China
Tianjin Crest Pharmaceutical R&D Co., Ltd. (Tianjin Yao Technology Development Co., Ltd.)(expird)
Contact:+86-22-66211386
Address:Building B5-405, No, 80 4th Avenue, TEDA, Tianjin, China P.R. 300457
Doi:10.1039/c5ob00472a
(2015)Doi:10.1016/S0040-4039(01)83177-4
(1977)Doi:10.1021/ja00498a023
(1979)Doi:10.1055/s-1977-24612
(1977)Doi:10.1246/bcsj.74.2433
(2001)Doi:10.1016/j.bmc.2005.06.039
(2005)