Radical intermediates in the photorearrangement of 3-hydroxyindolic nitrones

被引：5

作者：

Alberti, Angelo ^{[2
]}

Astolfi, Paola ^{[1
]}

Carloni, Patricia ^{[1
]}

Doepp, Dietrich ^{[3
]}

Greci, Lucedio ^{[1
]}

Rizzoli, Corrado ^{[4
]}

Stipa, Pierluigi ^{[1
]}

机构：

[1] Univ Politecn Marche, Dipartimento ISAC, Sez Chim, I-60131 Ancona, Italy

[2] Area Ric Bologna, CNR, ISOF, I-40129 Bologna, Italy

[3] Univ Duisburg Essen, Fachgebiet Organ Chem, D-45117 Essen, Germany

[4] Univ Parma, Dipartimentio Chim Gen Chim Analit & Chim Fis, I-43100 Parma, Italy

来源：

TETRAHEDRON | 2011年 / 67卷 / 36期

关键词：

Nitrone photochemistry; Oxaziridine intermediates; DFT calculations; EPR spectroscopy; Spin trapping; N-OXIDES; PHOTOCHEMICAL REACTIONS; PERTURBATION-THEORY; OXAZIRIDINES; DERIVATIVES; PHOTOLYSIS;

D O I：

10.1016/j.tet.2011.06.094

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A number of 3-hydroxy substituted indolic nitrones were found to quantitatively photorearrange to (2-benzoylamino)phenyl ketones upon UV-A irradiation. EPR-Spin Trapping experiments suggest that the process, which is believed to proceed via the formation of an oxaziridine, follows a homolytic pathway. Although DFT calculations do not allow to totally exclude alternative routes involving singlet intermediates, they do provide support to the proposed homolytic mechanism, which would be driven by a 1,5-hydrogen transfer subsequent to the oxaziridine ring opening. When this hydrogen transfer was made impossible by methylation of the 3-OH group, a benzoxazine was isolated as the sole reaction product. (C) 2011 Elsevier Ltd. All rights reserved.

引用

页码：6889 / 6894

页数：6

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