Tuning the strain effect to induce selectivity through intramolecular nitrene insertion into an adjacent methoxy C-H bond leading to form a new benzoxazole: experimental and computational studies

被引：1

作者：

Eswaran, Sambasivan V. ^{[1
]}

Kaur, Divneet ^{[2
]}

Khamaru, Krishnendu ^{[5
]}

Prabhakar, Sripadi ^{[3
]}

Sony, T. ^{[3
]}

Raghunathan, Partha ^{[4
]}

Ganguly, Bishwajit ^{[5
]}

机构：

[1] UNESCO DBT Reg Ctr Biotechnol, Faridabad 121004, Haryana, India

[2] CSIR Inst Genom & Integrat Biol, Mathura Rd Campus, Delhi 110025, India

[3] Indian Inst Chem Technol, Natl Ctr Mass Spectrometry, Hyderabad 500607, Andhra Pradesh, India

[4] Natl Brain Res Inst, Manesar 122050, Haryana, India

[5] CSIR Cent Salt & Marine Chem Res Inst, Computat & Simulat Unit, Analyt Discipline & Centralized Instrument Facil, Bhavnagar 364002, Gujarat, India

来源：

TETRAHEDRON LETTERS | 2016年 / 57卷 / 17期

关键词：

Pyrolysis; Nitrene; Oxazolidine; DFT study; Strain effect; LASER FLASH-PHOTOLYSIS; RING-EXPANSION; CHEMISTRY; AZIDES; PHOTOCHEMISTRY; SPECTROSCOPY; DERIVATIVES; METHYL; META;

D O I：

10.1016/j.tetlet.2016.03.061

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Pyrolysis of azido-meta-meconine yields only a single product 1D, which has been characterized spectro-scopically (H-1 NMR, C-13 NMR, HSQC, DEPT & MS). These results reveal that the fused five-member lactone ring can influence the product selectivity. The DFT calculations suggest the formation of favourable oxazolidine intermediate compared to azirine (1Z) and ketenimine (1H) intermediates. The isodesmic analysis showed that the fused lactone aryl nitrene (1N) would have more strain to form azirine (1Z) intermediate than the corresponding aryl nitrene (1M). (C) 2016 Elsevier Ltd. All rights reserved.

引用

页码：1899 / 1902

页数：4

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