BREDTS RULE
BREDTS RULE
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DOI：
10.1039/cs9740300041
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发表时间：
1974-01-01
影响因子：
46.2
通讯作者：
BUCHANAN, GL
中科院分区：
文献类型：
--
作者：
BUCHANAN, GL
在L漫长而卓有成效的工作生涯中，朱利叶斯·布莱特对结构化学和立体化学做出了几项重要贡献。例如，我们归功于他的樟脑的桥联双环结构和异构化的概念。但今天，人们记住他的主要原因是以他的名字命名的一条规则--榄烷(1)和蒎烷(2)系列的化合物不能在桥头处有双键。这一简单的真理很容易被分子模型验证，但在二维图中可以忽略它，因此它在有机化学中作为一条有用的经验法则而存在，经验上但可靠。最近，对它所依据的证据的关键重新审查引起了怀疑，实际上，自那以后合成了几个以前被归类为禁用的桥头烯。这些成功提出了一个问题，布莱特的规则仍然有效吗？他们还催生了对在应变双键中起作用的应力因素的评估。这篇评论是在布莱特提出他的规则仅仅50年后进行的，总结和评估了它所基于的早期证据，并试图展示我们目前对压力的理解如何使我们能够将其置于更广泛的背景下。
In a long and fruitful working life, l which was centred very largely around the chemistry of camphor, Julius Bredt made several important contributions to structural chemistry and stereo-chemistry. For example, we owe to him the bridged bicyclic structure of camphor and the concept of exolendo isomerism. But today he is remembered chiefly for the rule that bears his name-compounds of the camphane (1) and pinane (2) series cannot have a double bond at the bridgehead.This simple truth can be verified readily by molecular models but it can be overlooked in a two-dimensional drawing and so it has survived in organic chemistry as a useful rule of thumb, empirical but reliable. More recently, a critical re-examination of the evidence upon which it rests has raised doubts, and indeed severaI bridgehead alkenes which were previously classified as forbidden have since been synthesized. These successes raise the question, is Bredt’s rule still valid? They have also precipitated an appraisal of the stress factors which are operative in strained double bonds. This review, which comes just 50 years after Bredt propounded his rule, summarizes and assesses the early evidence upon which it was based and attempts to show how our present understanding of strain enables us to set it in a wider context.