Enantioselective radical cyclisation reactions of 4-substituted quinolones mediated by a chiral template

被引：37

作者：

Bakowski, Aline ^{[1
]}

Dressel, Martina ^{[1
]}

Bauer, Andreas ^{[1
]}

Bach, Thorsten ^{[1
]}

机构：

[1] Tech Univ Munich, Lehrstuhl Organ Chem 1, D-85747 Garching, Germany

来源：

ORGANIC & BIOMOLECULAR CHEMISTRY | 2011年 / 9卷 / 09期

关键词：

2+2 PHOTOCYCLOADDITION REACTIONS; ASYMMETRIC THERMAL-REACTIONS; GENERATED O-QUINODIMETHANE; QUATERNARY AMMONIUM-SALTS; NORRISH-YANG CYCLIZATION; MOLECULAR RECOGNITION; PHOTOCHEMICAL-REACTIONS; ADDITION REACTIONS; ORGANIC-SYNTHESIS; HOST;

D O I：

10.1039/c0ob01272f

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Six 4-substituted quinolones 6-8, which bear an omega-iodoalkyl chain, were prepared and subjected to reductive radical cyclisation conditions employing BEt3/O-2 as the initiator and either Bu3SnH or TMS3SiH as hydride source. 4-(4-Iodobutyl)-quinolone (6a) and 4-(3-iodopropylthio)-quinolone (8a) gave the respective 6-endo-cyclisation products in good yields. 4-(3,3-Dimethyl-4-iodobutyl)-quinolone (6b) cyclised in a 5-exo-fashion, while the other substrates delivered only reduction products. The cyclisation reactions could be conducted in the presence of a chiral template (1) with high enantiomeric excess (94-99% ee). The association behaviour of substrate 6a to 1 was studied by NMR titration experiments. In the enantioselective cyclisation of 6b a significant nonlinearity was observed when comparing the product ee with the ee of the template.

引用

页码：3516 / 3529

页数：14

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