Dead Ends and Detours En Route to Total Syntheses of the 1990s
Dead Ends and Detours En Route to Total Syntheses of the 1990s
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20 世纪 90 年代全合成的死胡同和弯路
DOI：
10.1002/chin.200028257
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发表时间：
2000
期刊：
影响因子：
--
通讯作者：
M. C. Torre
中科院分区：
文献类型：
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作者：
M. Sierra;M. C. Torre
从一开始，有机化学和全合成就紧密地结合在一起。事实上，有机化学新生首先学习的事情之一就是如何将两个分子连接在一起以获得更复杂的分子。当然，他们要成为完全成熟的合成化学家还有很长的路要走，但他们必须具备构建分子的基本本能，因为合成是有机化学的本质。随着化学界对有机合成科学（艺术，或两者）成熟的不同观点的共存，很明显，现在我们知道如何分离出几乎所有最复杂的分子。首要的问题是它有多容易实现？对于描述简单或复杂分子的全合成的论文的读者来说，似乎所遵循的路线在大多数情况下都是顺利的，没有麻烦。写在纸上的合成方案显然是在实验室中进行的，几乎没有修改，如果有的话，这些修改基本上似乎是基于找到实现所需反应的最佳实验条件。计划的合成方案未能实现目标，意外的反应性所造成的弯路，或缺乏反应性几乎从未讨论过，因为它们可能会降低报告工作的价值。这篇评论试图从不同的角度来看待全合成;它将集中在合成工作中发现的问题，这些问题会导致偏离原始合成计划，或者最终可能迫使重新设计的死胡同。从那里，从原始路线到最终成功实现合成目标的路线的演变将被呈现。选择本文中讨论的合成是因为它们包含关于原始合成计划失败的明确信息，以及目标分子最终路线的演变。因此，它们包含了许多有用的负面信息，否则可能会丢失。
From the very beginning organic chemistry and total synthesis have been intimately joined. In fact, one of the first things that freshmen in organic chemistry learn is how to join two molecules together to obtain a more complex one. Of course they still have a long way to go to become fully mature synthetic chemists, but they must have the primary instinct to build molecules, as synthesis is the essence of organic chemistry. With the different points of view that actually coexist in the chemical community about the maturity of the science (art, or both) of organic synthesis, it is clear that nowadays we know how to make almost all of the most complex molecules ever isolated. The primary question is how easy is it to accomplish? For the readers of papers describing the total synthesis of either simple or complex molecules, it appears that the routes followed are, most of the time, smooth and free of troubles. The synthetic scheme written on paper is, apparently, done in the laboratory with few, if any, modifications and these, essentially, seem to be based on finding the optimal experimental conditions to effect the desired reaction. Failures in the planned synthetic scheme to achieve the goal, detours imposed by unexpected reactivity, or the absence of reactivity are almost never discussed, since they may diminish the value of the work reported. This review attempts to look at total synthesis from a different side; it will focus on troubles found during the synthetic work that cause detours from the original synthetic plan, or on the dead ends that eventually may force redesign. From there, the evolution from the original route to the final successful one that achieves the synthetic target will be presented. The syntheses discussed in this paper have been selected because they contain explicit information about the failures of the original synthetic plan, together with the evolution of the final route to the target molecule. Therefore, they contain a lot of useful negative information that may otherwise be lost.