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首页> 外文期刊>Chemistry: A European journal >Total Synthesis of the turrianes and Evaluation of Their DNA-Cleaving Properties
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Total Synthesis of the turrianes and Evaluation of Their DNA-Cleaving Properties

机译：turrianes的全合成及其DNA切割性能的评估

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摘要

The first toal synthesis of three nautrally occurring cyclphane derivatives belonging to the turriane family of natural products is described. Their sterically hindered biaryl entity is formed by reaction of the Grignard reagent derived from aryl bromide 10 with the oxazoline derivative 18, and the macrocyclic tether of the targets is efficiently forged by ring closing metathesis. while conventional RCM catalyzed by the ruthenium-carbene complexes 33 or 34 invariably leads to the formation of miztures of both stereoisoemrs with the undesirable (E)-alkene prevailing, ring closing alkyne metathesis (RCAM) followed by Lindlar reduction of the resulting cycloalkynes 37 and 38 opens a convenient and stereoselectrive entry into this class of compounds. RCAM can either be accomplished by using the tungsten alkylidyne complex [(tBuO)_3Wident toCCMe_3] or by means of a catalyst formed in situ from [Mo(CO)_6] and para-trifluoromethylphenol. The latter method is significantly accelerated when carried out under microwave heating. Furthermore, the judicious choice of the protecting groups for the phenolic-OH functions turned out ot bve crucial. PMB-ethers were found to be compatible with the diverse reaction conditions en route to 3-5; their cleavage, however, had to be carried out under carefully optimized conditions to minimize competing O-C PMB migration. Turrianes 3-5 are shown to be potent DNA cleaving agents under oxidative conditions when administered in the presence of copper ions.
机译：描述了属于天然产物turriane家族的三种天然存在的环烷衍生物的首次全合成。它们的位阻联芳基实体是由衍生自芳基溴化物10的格氏试剂与恶唑啉衍生物18反应而形成的，靶的大环系链通过闭环易位而有效地锻造。钌-卡宾配合物33或34催化的传统RCM总是导致两个立体异构体的混合物形成，其中不受欢迎的（E）-烯烃占优势，闭环炔烃复分解（RCAM），然后Lindlar还原生成的环炔烃37和38打开了方便且立体选择的类化合物的入口。 RCAM可以通过使用亚烷基钨配合物[（tBuO）_3Wate to CCMe_3]或通过由[Mo（CO）_6]和对三氟甲基苯酚原位形成的催化剂来完成。当在微波加热下进行时，后一种方法被大大加速。此外，对于酚-OH官能团的保护基的明智选择是至关重要的。发现PMB-醚与至3-5的各种反应条件均相容。然而，它们的切割必须在精心优化的条件下进行，以最大程度地减少竞争性O-C PMB迁移。当在铜离子存在下施用时，Turrianes 3-5被证明在氧化条件下是有效的DNA裂解剂。

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