From tartrate to taxoids: A double, intramolecular Diels-Alder strategy
From tartrate to taxoids: A double, intramolecular Diels-Alder strategy
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DOI：
10.1351/pac199769030495
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发表时间：
1997-03-01
影响因子：
1.8
通讯作者：
Fallis, AG
中科院分区：
文献类型：
--
作者：
Fallis, AG
概述了各种分子内[4 + 2]环加成策略，以最终合成有效的抗肿瘤药物紫杉醇（Taxol(R)）。最初的模型研究采用取代的环己烯来保持亲二烯和二烯的接近，以产生必要的三环[9.3.1.0(3,8)]五烯骨架。环A构建块和适当的二烯的路线已经发展并详细阐述为更高取代的diols - alder前体。不幸的是，这些未能环化，因此选择了一种新的策略，其中酒石酸盐“系链对照组”既指导初始环加成到取代的十氢化萘，又赋予所需的不对称性。环裂解后的选择性官能团操作将提供一种新的二烯-亲二烯化合物组合，通过刘易斯酸催化的环加成可以构建所需的三环核。
Various intramolecular [4 + 2] cycloaddition strategies directed toward the eventual total synthesis of the potent anti tumor agent paclitaxel (Taxol(R)) are outlined. The initial model studies employed a substituted cyclohexene to hold the dienophile and the diene in proximity for the cycloaddition to yield the requisite tricyclo[9.3.1.0(3,8)]pentadecene skeleton. Routes to ring A building blocks and the appropriate dienes have been developed and elaborated into more highly substituted Diels-Alder precursors. Unfortunately, these failed to cyclize and a new strategy has been selected in which a tartrate ''tether control group'' both directed the initial cycloaddition to a substituted decalin and imparted the required asymmetry. Ring cleavage followed by selective functional group manipulation will afford a new diene-dienophile combination from which the desired tricyclic nucleus may be constructed by Lewis acid catalyzed cycloaddition.