An Asymmetric Approach towards (-)-Aphanorphine and Its Analogues

被引：33
作者：
Donets, Pavel A. [1 ]
Goeman, Jan L. [2 ]
Van der Eycken, Johan [2 ]
Robeyns, Koen
Van Meervelt, Luc
Van der Eycken, Erik V. [1 ]
机构：
[1] Katholieke Univ Leuven, Lab Organ & Microwave Assisted Chem LO MAC, Dept Chem, B-3001 Louvain, Belgium
[2] Univ Ghent, Lab Organ & Bioorgan Synth, Dept Chem, B-9000 Ghent, Belgium
来源：
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2009年 / 2009卷 / 06期
关键词：
Alkaloids; Asymmetric catalysis; Heck reaction; Radical reactions; Cyclization; FORMAL SYNTHESIS; (+)-APHANORPHINE; PALLADACYCLES; CATALYSTS; EFFICIENT; ESTERS; ROUTE;
D O I：
10.1002/ejoc.200801175
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
A short enantioselective approach towards the alkaloid (-)-aphanorphine and its substituted analogues is described. The enantiomerically pure starting material for the synthesis was obtained by asymmetric hydrogenation in the presence of the Rh-(S)-PipPhos complex. Microwave-assisted Heck cyclization selectively provided the seven-membered 3-benzazepine ring. Further, the assembly of the tricyclic core of the alkaloid was accomplished by intramolecular radical cyclization. The X-ray structure confirming the absolute configuration of the obtained products is described. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
引用
收藏
页码：793 / 796
页数：4
相关论文
共 22 条
  • [1] DESILYLATION OF ALPHA-TRIMETHYLSILYLMETHYLENE-GAMMA-LACTONES - A NEW ROUTE TO ALPHA-METHYLENE-GAMMA-LACTONES
    BACHI, MD
    BOSCH, E
    [J]. TETRAHEDRON LETTERS, 1988, 29 (21) : 2581 - 2584
  • [2] PipPhos and MorfPhos: Privileged monodentate phosphoramidite ligands for rhodium-catalyzed asymmetric hydrogenation
    Bernsmann, H
    van den Berg, M
    Hoen, R
    Minnaard, AJ
    Mehler, G
    Reetz, MT
    De Vries, JG
    Feringa, BL
    [J]. JOURNAL OF ORGANIC CHEMISTRY, 2005, 70 (03) : 943 - 951
  • [3] Cyclic sulfamidates as versatile lactam precursors. An evaluation of synthetic strategies towards (-)-aphanorphine
    Bower, John F.
    Szeto, Peter
    Gallagher, Timothy
    [J]. ORGANIC & BIOMOLECULAR CHEMISTRY, 2007, 5 (01) : 143 - 150
  • [4] Efficient synthesis of the 3-benzazepine framework via intramolecular heck reductive cyclization
    Donets, Pavel A.
    Van der Eycken, Erik V.
    [J]. ORGANIC LETTERS, 2007, 9 (16) : 3017 - 3020
  • [5] Total synthesis of (±)-lennoxamine and (±)-aphanorphine by intramolecular electrophilic aromatic substitution reactions of 2-amidoacroleins
    Fuchs, JR
    Funk, RL
    [J]. ORGANIC LETTERS, 2001, 3 (24) : 3923 - 3925
  • [6] Formal synthesis of (-)-aphanorphine using seqnential photomediated radical reactions of dithiocarbamates
    Grainger, Richard S.
    Welsh, Emma J.
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (28) : 5377 - 5380
  • [7] APHANORPHINE, A NOVEL TRICYCLIC ALKALOID FROM THE BLUE-GREEN-ALGA APHANIZOMENON-FLOS-AQUAE
    GULAVITA, N
    HORI, A
    SHIMIZU, Y
    LASZLO, P
    CLARDY, J
    [J]. TETRAHEDRON LETTERS, 1988, 29 (35) : 4381 - 4384
  • [8] Herrmann W. A., 1995, ANGEW CHEM, V107, P1989
  • [9] Palladacycles: Efficient new catalysts for the Heck vinylation of aryl halides
    Herrmann, WA
    Brossmer, C
    Reisinger, CP
    Riermeier, TH
    Ofele, K
    Beller, M
    [J]. CHEMISTRY-A EUROPEAN JOURNAL, 1997, 3 (08) : 1357 - 1364
  • [10] PALLADACYCLES AS STRUCTURALLY DEFINED CATALYSTS FOR THE HECK OLEFINATION OF CHLOROARENES AND BROMOARENES
    HERRMANN, WA
    BROSSMER, C
    OFELE, K
    REISINGER, CP
    PRIERMEIER, T
    BELLER, M
    FISCHER, H
    [J]. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH, 1995, 34 (17): : 1844 - 1848
123