STEREOCHEMICAL ASPECTS OF THE INTRAMOLECULAR DIELS-ALDER REACTION
STEREOCHEMICAL ASPECTS OF THE INTRAMOLECULAR DIELS-ALDER REACTION
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DOI：
10.1039/cs9871600187
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发表时间：
1987-06-01
影响因子：
46.2
通讯作者：
CRAIG, D
中科院分区：
文献类型：
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作者：
CRAIG, D
Diels-Alder反应自60多年前被发现以来，已成为有机化学中最常用的反应策略之一。以高度立体选择性和很大程度上可预测的方式同时产生多达四个手性中心的能力导致其应用于许多合成挑战，这些挑战通常难以通过其他手段获得。这个过程的分子内版本，虽然比它的双分子对应物年轻30多年，2同样在具有高水平立体控制的多环体系的构建中得到了广泛的应用。分子内Diels-Alder（IMDA）反应，这些在很大程度上简单地编目了已发表的反应实例，根据诸如二烯和亲二烯基团上的取代基的性质、连接链中取代基的性质和存在以及连接链中杂原子基团的掺入等结构特征对环化底物进行分类。本审查的IMDA反应的立体化学的结果，包括一些最近的理论工作在该地区的简要讨论，这些参数的影响进行了严格评估。虽然它显然是详尽分析所有已知的IMDA反应的例子在本审查的范围之外，特别强调已被放置在那些情况下，观察到的反应性，以突出和强调一个新兴的立体化学趋势。作为这种选择性分析的必然结果，其中立体化学不明显的反应的例子，或者其中观察到的选择性结果纯粹是由于一些明显的结构特征而被省略。在类固醇合成中使用IMDA反应，在其他地方进行了充分的综述，但没有详细介绍。由于最后一次主要综述出现在1984年，因此对自该日期以来的所有相关文献进行了综述。
Since its discovery nearly 60 years ago,’the Diels-Alder reaction has become one of the most commonly used stratagems in organic chemistry. The ability to generate simultaneously up to four chiral centres in a highly stereoselective and largely predictable fashion has resulted in its application to numerous synthetic challenges, often difficultly accessible by other means. The intramolecular version of this process, although over thirty years younger than its bimolecular counterpart, 2 has similarly enjoyed widespread use in the construction of polycyclic ring systems with high levels of stereocontrol.Whilst the last ten years have seen a large number of additions to the review literature covering the. intramolecular Diels-Alder (IMDA) rea~ tion,~ these have largely simply catalogued published examples of the reaction, classifying cyclization substrates according to such structural features as the nature of substituents on the diene and dienophilic groups, the nature and presence of substituents in the linking chain, and the incorporation of heteroatomic groups in the linking chain. The present review sets out to assess critically the effect of such parameters on the stereochemical outcome of the IMDA reaction, including a brief discussion of some recent theoretical work in the area. Although it is clearly outside the scope of this review to analyse exhaustively all the known examples of the IMDA reaction, particular emphasis has been placed on those instances where the observed reactivity serves to highlight and exemplify an emerging stereochemical trend. As a corollary of this selective analysis, examples of the reaction in which stereochemistry is not apparent, or where the observed selectivity results purely as a consequence of some obvious structural feature have been omitted. The use of the IMDA reaction in steroid synthesis, amply reviewed elsewhere, has not been covered in detail. Because the last major reviews appeared in 1984, all the relevant literature since that date has been reviewed.