Efficient switching from the 2,3′- to 2,2′-bipyrrole scaffold via the recyclization of 1-(benzoylmethylanilino)-3-imino-3H-2-cyanopyrrolizines: Crucial effect of the DBU organic superbase

被引：7
|
作者：
Trofimov, Boris A. [1 ]
Sagitova, Elena F. [1 ]
Petrova, Olga V. [1 ]
Sobenina, Lyubov N. [1 ]
Ushakov, Igor A. [1 ]
Vashchenko, Alexander V. [1 ]
机构：
[1] Russian Acad Sci, Siberian Branch, AE Favorsky Irkutsk Inst Chem, 1 Favorsky Str, Irkutsk 664033, Russia
来源：
TETRAHEDRON LETTERS | 2017年 / 58卷 / 23期
关键词：
1-(Benzoylmethylanilino)-3-imino-3H-2-cyanopyrrolizines; 2,2 '-Bipyrroles; DBU; Heterocycles; KOH/DMSO superbase system; EXPANDED PORPHYRIN; PRODIGIOSIN; RING; INTERMEDIATE; BIPYRROLES; BINDING;
D O I：
10.1016/j.tetlet.2017.04.065
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
The recyclization of readily available 1-(benzoylmethylanilino)-3-imino-3H-2-cyanopyrrolizines using the DBU organic superbase, unexpectedly gave 2,2'-bipyrroles with amino, keto and cyano functional groups on one of the pyrrole rings in 83-94% yield. Previously, using the KOH/DMSO system, this recyclization led to 2,3'-bipyrroles in low yields (12-26%). This selective switching was explained by sterically hindered access for the intermediate carbanion to the 1-position of the pyrrolizine ring due to the large size of the accompanying DBU countercation. The new methodology opens an efficient route to pharmaceutically and synthetically useful densely functionalized 2,2'-bipyrroles. (C) 2017 Elsevier Ltd. All rights reserved.
引用
收藏
页码：2209 / 2212
页数：4
相关论文
共 50 条
  • [1] Synthesis of functionalized 2,2′- and 2,3′-bipyrroles via 3-imino-3H-pyrrolizine-2-carbonitriles
    Petrova, Olga V.
    Sagitova, Elena F.
    Sobenina, Lyubov N.
    Ushakov, Igor A.
    Borodina, Tat'yana N.
    Smirnov, Vladimir I.
    Trofimov, Boris A.
    TETRAHEDRON LETTERS, 2016, 57 (32) : 3652 - 3656
  • [2] Recyclization of 2-imino-2H-1-benzopyrans with nucleophilic reagents -: Reaction of 2-iminocoumarin-3-carboxamides with 2-aminothiophene-3-carboxamides
    Kovalenko, SM
    Vlasov, SV
    Chernykh, VP
    SYNTHESIS-STUTTGART, 2006, (05): : 847 - 852
  • [3] DBU as a scaffold for the synthesis of [1,3]oxazolo[2′,3′:2,3]pyrimido[ 1,2-a]azepines: annulation with aromatic cyanopropargylic alcohols
    Shemyakina, Olesya A.
    Volostnykh, Ol'ga G.
    Stepanov, Anton V.
    Mal'kina, Anastasiya G.
    Ushakov, Igor A.
    Apartsin, Konstantin A.
    Kireeva, Victoriya V.
    Trofimov, Boris A.
    MENDELEEV COMMUNICATIONS, 2018, 28 (02) : 128 - 130
  • [4] Cyclization of 1-(4,4-diethoxybutyl)-3-aryl(thio)ureas to 2-arylpyrrolidines and 2,3´-bipyrrole derivatives
    A. V. Smolobochkin
    A. S. Gazizov
    Yu. K. Voronina
    A. R. Burilov
    M. A. Pudovik
    Russian Chemical Bulletin, 2016, 65 : 731 - 734
  • [5] 1-(2,2'-BIPYRIDYL)-2-METHYL-3-(TRIMETHYLSILYL)-2,3-DICARBA-1-STANNA-CLOSO-HEPTABORANE(6)
    SIRIWARDANE, U
    HOSMANE, NS
    CHU, SSC
    ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS, 1987, 43 : 1067 - 1069
  • [6] 1-(2,2'-BIPYRIDINE)-2-METHYL-3-(TRIMETHYLSILYL)-2,3-DICARBA-1-PLUMBA-CLOSO-HEPTABORANE(6)
    SIRIWARDANE, U
    LU, KJ
    HOSMANE, NS
    ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS, 1990, 46 : 1391 - 1394
  • [7] 1-(2,2'-6',2''-TERPYRIDINE)-2-METHYL-3-TRIMETHYLSILYL-2,3-DICARBA-1-STANNA-CLOSO-HEPTABORANE(6)-2,2'-6',2''-TERPYRIDINE
    SIRIWARDANE, U
    HOSMANE, NS
    ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS, 1988, 44 : 1572 - 1576
  • [8] Recent advances in organic crystal engineering with the 1,1",3,3"-Tetrahydro-dispiro[2H-indene-2,2′-piperazine-5′,2"-(2H)indene]-3′,6′-dione scaffold
    Murigi, Francis N.
    Mash, Eugene A.
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2010, 239
  • [9] 2,2'—二苯基—[2,3'—联—1H—吲哚]—3(2H)—酮的过氧酸氧化反应
    凌可庆
    淮北师范大学学报(自然科学版), 1997, (01) : 42 - 44
  • [10] VERSATILE SYNTHESIS OF STEREOSPECIFICALLY LABELED D-AMINO ACIDS VIA LABELED AZIRIDINES - PREPARATION OF (2R,3S)-[3-H-2(1)]-SERINE AND (2R,3R)-[2,3-H-2(2)]-SERINE (2S,2'S,3S,3'S-[3,3'-H-2(2)]-CYSTINE AND (2S,2'S,3R,3'R)-[2,2',3,3'-H-2(4)]-CYSTINE AND (2S,3S)-[3-H-2(1)-] AND (2S,3R)-[2,3-H-2(2)]-BETA-CHLOROALANINE
    AXELSSON, BS
    OTOOLE, KJ
    SPENCER, PA
    YOUNG, DW
    JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1994, (07): : 807 - 815
12345