STEREOCONTROLLED SYNTHESIS OF (+/-)-DEBROMOAPLYSIN, (+/-)-APLYSIN, (+/-)-DEBROMOAPLYSINOL, (+/-)-APLYSINOL, AND (+/-)-ISOAPLYSIN

被引：28

作者：

BISWAS, S ^{[1
]}

GHOSH, A ^{[1
]}

VENKATESWARAN, RV ^{[1
]}

机构：

[1] INDIAN ASSOC CULTIVAT SCI,DEPT ORGAN CHEM,CALCUTTA 700032,W BENGAL,INDIA

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1990年 / 55卷 / 11期

关键词：

D O I：

10.1021/jo00298a022

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Stereocontrolled synthesis in racemic form of the title marine sesquiterpenes is described. Alkylation of styrenol 6 with a-bromopropanoic acid furnished acid 7. Similar alkylation with α-bromo-β-methoxypropanoic acid provided acid 8. Intramolecular cycloaddition of the ketene generated from the acid chloride of 7 afforded cyclobutanone 9 whereas 8 led to a mixture of 10 and 11, but following a modified condition 10 could be obtained exclusively. Regioselective ring expansion of 9 and 10 to cyclopentanones 13 and 15 followed by addition of methylmagnesium iodide and dehydration provided olefins 16 and 17. Hydrogenation of these using Pd-C catalyst lacked selectivity, but Pt02 showed selectivity, affording (±)-2 and 19, respectively. Controlled bromination of 2 furnished (±)-aplysin (1), and 19 yielded 21. Demethylation of 19 afforded (±)-debromoaplysinol (3). Similarly 21 furnished (±)-aplysinol (4). Bromination of 3 resulted in (±)-isoaplysin (5). © 1990, American Chemical Society. All rights reserved.

引用

页码：3498 / 3502

页数：5

共 22 条

[1] INTRAMOLECULAR (2 + 2) CYCLOADDITIONS OF PHENOXYKETENES [J].

BRADY, WT ;

GIANG, YF .

JOURNAL OF ORGANIC CHEMISTRY, 1985, 50 (25) :5177-5179

[2]

BRADY WT, 1987, SYNTHESIS-STUTTGART, P395

[3]

DIVAKAR KJ, 1976, SYNTHETIC COMMUN, P423

[4]

ERICKSON KL, 1978, MARINE NATURAL PRODU, V5

[5] STEREOCONTROLLED SYNTHESIS OF (+/-)-DEBROMOAPLYSIN AND (+/-)-APLYSIN [J].

GHOSH, A ;

BISWAS, S ;

VENKATESWARAN, RV .

JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1988, (21) :1421-1421

[6] PREPARATION AND REARRANGEMENT OF TRICHOTHECANE-LIKE COMPOUNDS - SYNTHESIS OF APLYSIN AND FILIFORMIN [J].

GOLDSMITH, DJ ;

JOHN, TK ;

KWONG, CD ;

PAINTER, GR .

JOURNAL OF ORGANIC CHEMISTRY, 1980, 45 (20) :3989-3993

[7] A PREFERRED INTRAMOLECULAR ENE REACTION BETWEEN KETENE AND OLEFIN [J].

KHER, SM ;

KULKARNI, GH ;

MITRA, RB .

SYNTHETIC COMMUNICATIONS, 1989, 19 (3-4) :597-604

[8]

KRAPCHO AP, 1982, SYNTHESIS-STUTTGART, V805, P893

[9] THE SHERADSKY REARRANGEMENT OF ALPHA,ALPHA'-DISUBSTITUTED CYCLOPENTANONE ARYLOXIMES - A SYNTHESIS OF THE SESQUITERPENES (+/-)-APLYSIN AND (+/-)-FILIFORMIN [J].

LARONZE, JY ;

ELBOUKILI, R ;

CARTIER, D ;

LARONZE, J ;

LEVY, J .

TETRAHEDRON LETTERS, 1989, 30 (17) :2229-2232

[10]

LIU HJ, 1973, TETRAHEDRON LETT, P4937

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