Kinetic Study of the Reaction of the Phthalimide-N-oxyl Radical with Amides: Structural and Medium Effects on the Hydrogen Atom Transfer Reactivity and Selectivity

被引：20

作者：

Bietti, Massimo ^{[3
]}

Forcina, Veronica ^{[1
,2
]}

Lanzalunga, Osvaldo ^{[1
,2
]}

Lapi, Andrea ^{[1
,2
]}

Martin, Teo ^{[1
,2
]}

Mazzonna, Marco ^{[1
,2
]}

Salamone, Michela ^{[3
]}

机构：

[1] Sapienza Univ Roma, Dipartimento Chim, Piazzale Aldo Moro 5, I-00185 Rome, Italy

[2] Sapienza Univ Roma, Dipartimento Chim, Ist CNR Metodol Chim IMC CNR, Sez Meccanismi Reaz, Piazzale Aldo Moro 5, I-00185 Rome, Italy

[3] Univ Tor Vergata, Dipartimento Sci & Tecnol Chim, Via Ric Sci 1, I-00133 Rome, Italy

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2016年 / 81卷 / 23期

关键词：

C-H BONDS; EFFICIENT AEROBIC OXIDATION; PI-STACKING INTERACTIONS; MOLECULAR-OXYGEN; ELECTRON-TRANSFER; METAL-FREE; MILD CONDITIONS; HYDROXYPHTHALIMIDE NHPI; AROMATIC-ALDEHYDES; CARBONYL-COMPOUNDS;

D O I：

10.1021/acs.joc.6b02482

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

A kinetic study of the hydrogen atom transfer (HAT) reactions from a series of secondary N-(4-X-benzyl)acetamides and tertiary amides to the phthalimide-N-oxyl radical (PINO) has been carried out. The results indicate that HAT is strongly influenced by structural and medium effects; in particular, the addition of Bronsted and Lewis acids determines a significant deactivation of C-H bonds a to the amide nitrogen of these substrates. Thus, by changing the reaction medium, it is possible to carefully control the regioselectivity of the aerobic oxidation of amides catalyzed by N-hydroxyphthalimide, widening the synthetic versatility of this process.

引用

页码：11924 / 11931

页数：8

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