Hernández Rosendo, León Elisa I, Moreno Pilar, Riesco-Fagundo Concepción, Suárez Ernesto
Instituto de Productos Naturales y Agrobiología del CSIC, Carretera de La Esperanza 3, 38206 La Laguna, Tenerife, Spain.
J Org Chem. 2004 Nov 26;69(24):8437-44. doi: 10.1021/jo049026p.
The synthesis of highly functionalized nitriles by an alkoxyl radical fragmentation of cyclic beta-hydroxy azides is described. The alkoxyl radicals were generated by reaction of the alcohols with (diacetoxyiodo)benzene and iodine under mild conditions compatible with the presence of sensitive substituents and the protective groups most frequently used in carbohydrate chemistry. To explore the scope and limitations of this methodology, experiments were carried out using a variety of beta-hydroxy azides of the carbohydrate (1-6, 33, and 41), monoterpenoid (21 and 22), and steroid (23-25) families of natural products. Of special interest are the aldopentonitriles (15-18, 34, and 42) and aldotetrononitriles (19 and 20) synthesized from the corresponding 2-azido-2-deoxycarbohydrates. To demonstrate the versatility of these aldononitriles as chiral synthons, 1,4-imino-1-deoxysugar (37) and 1,5-imino-1-deoxysugar (43) analogues of the polyhydroxypyrrolidine and -piperidine types were prepared.
描述了通过环状β-羟基叠氮化物的烷氧基自由基断裂合成高度官能化腈的方法。烷氧基自由基是通过醇与（二乙酰氧基碘）苯和碘在与敏感取代基以及碳水化合物化学中最常用的保护基兼容的温和条件下反应生成的。为了探索该方法的适用范围和局限性，使用了多种天然产物碳水化合物（1-6、33和41）、单萜（21和22）以及甾体（23-25）家族的β-羟基叠氮化物进行了实验。特别令人感兴趣的是由相应的2-叠氮基-2-脱氧碳水化合物合成的戊醛腈（15-18、34和42）和丁醛腈（19和20）。为了证明这些醛腈作为手性合成子的多功能性，制备了多羟基吡咯烷和哌啶类型的1,4-亚氨基-1-脱氧糖（37）和1,5-亚氨基-1-脱氧糖（43）类似物。
