Synthesis of 3D-Rich Heterocycles: Hexahydropyrazolo[1,5-a]pyridin2(1H)-ones and Octahydro-2H-2a,2a1-diazacyclopenta[cd]inden-2ones

被引：10

作者：

Kirar, Eva Pusavec ^{[1
]}

Drev, Miha ^{[1
]}

Mirnik, Jona ^{[1
]}

Groselj, Uros ^{[1
]}

Golobic, Amalija ^{[1
]}

Dahmann, Georg ^{[2
]}

Pozgan, Franc ^{[1
]}

Stefane, Bogdan ^{[1
]}

Svete, Jurij ^{[1
]}

机构：

[1] Univ Ljubljana, Fac Chem & Chem Technol, Vecna Pot 113, SI-1000 Ljubljana, Slovenia

[2] Boehringer Ingelheim Pharma GmbH & Co KG, Med Chem, D-88397 Biberach, Germany

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2016年 / 81卷 / 19期

关键词：

AZOMETHINE IMINES; 1,3-DIPOLAR CYCLOADDITIONS; DISTORTION/INTERACTION; REACTIVITY; DISCOVERY; CATALYSTS; AZINES; POTENT; METAL;

D O I：

10.1021/acs.joc.6b01608

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Two cyclic azomethine imines, 7-methyl- and 7-phenyl-2-oxo-Delta(7)-hexahydropyrazolo [1,5-a] pyridin-8-ium-1-ide, were prepared in seven steps from the respective commercially available delta-keto acids. The addition of Grignard reagents followed by N-alkylation at position 1 afforded the 1,7,7-trisubstituted hexahydropyrazolo [1,5-a] pyridin-2 (1H)-ones, whereas 1,3-dipolar cycloadditions of these dipoles to typical acetylenic and olefinic dip olarophiles gave 4a-substituted 2a,2a(1)-diazacyclopenta[cd]indene derivatives as the first representatives of a novel heterocyclic system. Regio- and stereoselectivity as well as the mechanism of these [3 + 2]-cycloadditions were evaluated using computational and experimental methods. The data obtained were in agreement with the polar concerted cycloaddition mechanism via the energetically favorable syn/endo-transition states.

引用

页码：8920 / 8933

页数：14

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