A Combined Experimental and Density Functional Theory Study on the Pd-Mediated Cycloisomerization of o-Alkynylnitrobenzenes - Synthesis of Isatogens and Their Evaluation as Modulators of ROS-Mediated Cell Death

被引：46

作者：

Ramana, Chepuri V. ^{[1
]}

Patel, Pitambar ^{[1
]}

Vanka, Kumar ^{[1
]}

Miao, Benchun ^{[2
]}

Degterev, Alexei ^{[2
]}

机构：

[1] Natl Chem Lab, Pune 411008, Maharashtra, India

[2] Tufts Univ, Dept Biochem, Boston, MA 02111 USA

来源：

EUROPEAN JOURNAL OF ORGANIC CHEMISTRY | 2010年 / 2010卷 / 31期

关键词：

Nitro-alkyne cycloisomerization; Cyclization; Palladium; Isatogens; Anthranil; Density functional calculations; MOLECULAR-OXYGEN; N-OXIDE; 2,2'-PYRIDYLISATOGEN TOSYLATE; CIS-CHLOROPALLADATION; WORKSTATION COMPUTERS; ALLOSTERIC MODULATOR; OXIDATION; MECHANISM; CYCLIZATION; ENERGY;

D O I：

10.1002/ejoc.201000769

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Highly selective cycloisomerization of o-alkynylnitrobenzenes, leading to isatogens, has been achieved by employment of a Pd-II complex. This reaction is very general and functional-group-tolerant. The possible mechanism of this reaction was investigated with the help of DFT calculations. Three possible pathways - namely, the addition of the nitro group either in (i) 5-exo-dig or (ii) 6-endo-dig mode and (iii) halopalladation - and subsequent intramolecular events have been considered and studied in detail. These investigations revealed that pathway (i) is the favored route to isatogen formation. A preliminary screening of the available isatogens reveals the 2-alkylisatogens to be novel ROS scavengers capable of inhibiting cellular necroptosis.

引用

页码：5955 / 5966

页数：12