Synthetic applications of 2-(1,3-dithian-2-yl)indoles .7. Synthesis of aspidospermidine

被引：58

作者：

Forns, P ^{[1
]}

Diez, A ^{[1
]}

Rubiralta, M ^{[1
]}

机构：

[1] UNIV BARCELONA,FAC FARM,LAB QUIM ORGAN,BARCELONA 08028,SPAIN

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1996年 / 61卷 / 22期

关键词：

D O I：

10.1021/jo9609900

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A new method of synthesizing the alkaloid aspidospermidine (1), based on building ring E on the pyridocarbazole [ABCD] ring structure, is reported. The preparation of the pyridocarbazole framework of Aspidosperma alkaloids is a new three-step synthetic application of 2-(1,3-dithian-2-yl)indoles. A tandem conjugate addition-alkylation reaction starting from indolyldithiane (4), 3-methylenelactam 8, and EtI yields the adduct 17. Treatment of lactam 17 with DIBALH leads to formation of the naphthyridoindole 18. Compound 18 isomerizes in aqueous AcOH to yield pyridocarbazole 3. Finally, closure of ring E and subsequent reduction of the dithiane ring produces aspidospermidine. Pyridocarbazoles 2 and 10 were prepared as models.

引用

页码：7882 / 7888

页数：7

共 21 条

[1] STUDIES ON THE SYNTHESIS OF PENTACYCLIC STRYCHNOS INDOLE ALKALOIDS - CLOSURE OF E-RING BY PUMMERER CYCLIZATION [J].

AMAT, M ;

BOSCH, J .

JOURNAL OF ORGANIC CHEMISTRY, 1992, 57 (21) :5792-5796

[2] A NEW STRATEGY FOR THE ENANTIOSELECTIVE SYNTHESIS OF ASPIDOSPERMA ALKALOIDS .2. ACHIEVEMENT OF THE PENTACYCLIC SYSTEM [J].

DESMAELE, D ;

DANGELO, J .

TETRAHEDRON LETTERS, 1990, 31 (06) :883-886

[3] SYNTHETIC APPLICATIONS OF 2-(1,3-DITHIAN-2-YL)INDOLES .4. NEW SYNTHESIS OF THE TETRACYCLIC ABED RING-SYSTEM OF STRYCHNOS ALKALOIDS [J].

DIEZ, A ;

CASTELLS, J ;

FORNS, P ;

RUBIRALTA, M ;

GRIERSON, DS ;

HUSSON, HP ;

SOLANS, X ;

FONTBARDIA, M .

TETRAHEDRON, 1994, 50 (22) :6585-6602

[4] INDOLE-2,3-QUINODIMETHANES - A NEW STRATEGY FOR THE SYNTHESIS OF TETRACYCLIC SYSTEMS OF INDOLE ALKALOIDS [J].

EXON, C ;

GALLAGHER, T ;

MAGNUS, P .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1983, 105 (14) :4739-4749

[5] Synthetic applications of 2-(1,3-dithian-2-yl)indoles .6. Synthesis of 20-epidasycarpidone [J].

Forns, P ;

Diez, A ;

Rubiralta, M ;

Solans, X ;

FontBardia, M .

TETRAHEDRON, 1996, 52 (10) :3563-3574

[6]

GROBELNY D, 1979, TETRAHEDRON LETT, P2639

[7]

JOULE JA, 1990, J CHEM RES MINIPRINT, P664

[8] ALPHA-METHYLENELACTAM REARRANGEMENT [J].

LEE, DL ;

MORROW, CJ ;

RAPOPORT, H .

JOURNAL OF ORGANIC CHEMISTRY, 1974, 39 (07) :893-902

[9] SYNTHESIS OF (+/-)-ASPIDOSPERMIDINE [J].

LEMENEZ, P ;

KUNESCH, N ;

LIU, S ;

WENKERT, E .

JOURNAL OF ORGANIC CHEMISTRY, 1991, 56 (08) :2915-2918

[10]

LOPEZ I, 1996, TETRAHEDRON, V52

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