Oxidative tandem alkoxide conjugate addition to nitroalkenes/radical 5-exo cyclizations-a versatile synthesis of functionalized 3-nitrotetrahydrofurans

被引：10

作者：

Jahn, Ullrich ^{[1
]}

Rudakov, Dmytro ^{[2
]}

Jones, Peter G. ^{[3
]}

机构：

[1] Acad Sci Czech Republ, Inst Organ Chem & Biochem, CR-16610 Prague 6, Czech Republic

[2] Tech Univ Carolo Wilhelmina Braunschweig, Inst Organ Chem, D-38106 Braunschweig, Germany

[3] Tech Univ Carolo Wilhelmina Braunschweig, Inst Anorgan & Analyt Chem, D-38106 Braunschweig, Germany

来源：

TETRAHEDRON | 2012年 / 68卷 / 05期

关键词：

Electron transfer; Oxidation; Radicals; Tandem reaction; Tetrahydrofurans; BOND-FORMING REACTIONS; OLEFIN CYCLOADDITION INOC; ONE-ELECTRON OXIDATION; ONE-POT SYNTHESIS; RADICAL CYCLIZATIONS; MICHAEL ADDITION; STEREOSELECTIVE-SYNTHESIS; DOMINO REACTIONS; COUPLING REACTIONS; ORGANIC-SYNTHESIS;

D O I：

10.1016/j.tet.2011.12.010

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Structurally diverse functionalized 4-(1-haloalkyl)-3-nitrotetrahydrofurans were conveniently obtained in moderate to good yield and moderate to very good diastereoselectivity by an oxidative tandem process consisting of conjugate addition reaction of lithium allyloxides to nitroalkenes followed by SET oxidation of the resulting nitronates. This triggers a radical cyclization; ligand transfer from the oxidant provides the products. The influence of the counter ion of the initial alkoxide and intermediate nitronate, the solvent and additives on the outcome of the tandem process was investigated. Optimal conditions for the tandem reactions consist of using butyllithium as the base for deprotonation in DME as the solvent. Cupric halides proved to be the SET oxidants of choice in the tandem reactions. A stereochemical model for the radical cyclization and ligand transfer steps is proposed. (C) 2011 Elsevier Ltd. All rights reserved.

引用

页码：1521 / 1539

页数：19

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