A concise total synthesis of the azaphenanthrene alkaloid eupolauramine

被引：59

作者：

Hoarau, C ^{[1
]}

Couture, A ^{[1
]}

Cornet, H ^{[1
]}

Deniau, E ^{[1
]}

Grandclaudon, P ^{[1
]}

机构：

[1] Univ Lille 1, UPRES A CNRS 8009, Chim Organ Phys Lab, F-59655 Villeneuve Dascq, France

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2001年 / 66卷 / 24期

关键词：

D O I：

10.1021/jo0105944

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A six-step total synthesis of the azaphenanthrene alkaloid eupolauramine 1 has been achieved using combinational metalation-cyclization tactics. The synthetic route involved first the construction of the azaisoindolinone 9 by aryne-mediated cyclization of he phosphorylated pyridocarboxamide 7 and subsequent dephosphorylation. Metalation of 9 followed by connection of the hydroxybenzyl appendage and E1CB anti-elimination allowed the formation of the halogenoarylmethylene azaisoindolinone 4 in the exclusive E-form. Oxidative radical cyclization gave rise to the azaphenanthrene skeleton and regioselective bromination of 3 induced the incorporation of the bromine atom at the 6-position of the azaphenanthrene lactam. Ultimate replacement of the bromine atom of 2 by the methoxy functionality by sequential transmetalation, in situ oxidation, and O-methylation of the phenolic derivative 14 completed the synthesis of the target natural product eupolauramine.

引用

页码：8064 / 8069

页数：6

共 41 条

[1] SYNTHESIS OF PYRROLO[3,4-C]PYRIDINES VIA PYRIDINE INTERMEDIATES [J].

AHMED, I ;

CHEESEMAN, GWH ;

JAQUES, B .

TETRAHEDRON, 1979, 35 (09) :1145-1149

[2] METAL IONS AND COMPLEXES IN ORGANIC REACTIONS .9. COPPER(1)-CATALYSED CONVERSION OF ARYL HALIDES INTO ALKYL ARYL ETHERS [J].

BACON, RGR ;

RENNISON, SC .

JOURNAL OF THE CHEMICAL SOCIETY C-ORGANIC, 1969, (02) :312-&

[3] THE TERTIARY AMIDE AS AN EFFECTIVE DIRECTOR OF ORTHO LITHIATION [J].

BEAK, P ;

BROWN, RA .

JOURNAL OF ORGANIC CHEMISTRY, 1982, 47 (01) :34-46

[4] MOLECULAR AND CRYSTAL-STRUCTURE OF EUPOLAURAMINE, A NOVEL TYPE OF ALKALOID FROM EUPOMATIA-LAURINA [J].

BOWDEN, BF ;

FREEMAN, HC ;

JONES, RDG .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1976, (06) :658-662

[5] CONSTITUENTS OF EUPOMATIA SPECIES .2. ISOLATION AND STRUCTURE DETERMINATION OF FURTHER EUPOMATENOID LIGNANS FROM BARK OF EUPOMATIA-LAURINA [J].

BOWDEN, BF ;

TAYLOR, WC ;

RITCHIE, E .

AUSTRALIAN JOURNAL OF CHEMISTRY, 1972, 25 (12) :2659-&

[6] ESTERS ARE EFFECTIVE COCATALYSTS IN COPPER-CATALYZED METHANOLYSIS OF ARYL BROMIDES [J].

CAPDEVIELLE, P ;

MAUMY, M .

TETRAHEDRON LETTERS, 1993, 34 (06) :1007-1010

[7]

Chang Z.-L., 1978, The Alkaloids, V31, P29

[8] PREPARATION OF THE 4 REGIOISOMERIC 2-(METHYLTHIO)OXAZOLOPYRIDINES - USEFUL SYNTHONS FOR ELABORATION TO 2-(AMINO SUBSTITUTED)OXAZOLOPYRIDINES [J].

CHUMOYER, MY ;

BERGER, R .

JOURNAL OF ORGANIC CHEMISTRY, 1995, 60 (17) :5721-5725

[9] PHOTOCYCLIZATION IN AN ALCOHOL SOLUTION CONTAINING DISSOLVED BASE - A NEW DEVELOPMENT IN ENAMIDE PHOTOCHEMISTRY [J].

COUTURE, A ;

GRANDCLAUDON, P ;

HOOIJER, SO .

JOURNAL OF ORGANIC CHEMISTRY, 1991, 56 (16) :4977-4980

[10] LDA-induced metalation of isoindolinones. An efficient route to 3-substituted isoindoline derivatives [J].

Couture, A ;

Deniau, E ;

Ionescu, D ;

Grandclaudon, P .

TETRAHEDRON LETTERS, 1998, 39 (16) :2319-2320

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