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Palladium-catalysed C-H activation of aliphatic amines to give strained nitrogen heterocycles

机译：钯催化脂肪族胺的C-H活化，得到应变氮杂环

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摘要

The development of new chemical transformations based on catalytic functionalization of unactivated C-H bonds has the potential to simplify the synthesis of complex molecules dramatically. Transition metal catalysis has emerged as a powerful tool with which to convert these unreactive bonds into carbon-carbon and carbon-heteroatom bonds, but the selective transformation of aliphatic C-H bonds is still a challenge. The most successful approaches involve a 'directing group', which positions the metal catalyst near a particular C-H bond, so that the C-H functionalization step occurs via cydometallation. Most directed aliphatic C-H activation processes proceed through a five-membered-ring cydometallated intermediate. Considering the number of new reactions that have arisen from such intermediates, it seems likely that identification of distinct cyclo-metallation pathways would lead to the development of other useful chemical transformations. Here we report a palladium-catalysed C-H bond activation mode that proceeds through a four-membered-ring cyclopalladation pathway. The chemistry described here leads to the selective transformation of a methyl group that is adjacent to an unprotected secondary amine into a synthetically versatile nitrogen heterocycle. The scope of this previously unknown bond disconnection is highlighted through the development of C-H animation and carbonylation processes, leading to the synthesis of aziridines and β-lactams (respectively), and is suggestive of a generic C-H functionalization platform that could simplify the synthesis of aliphatic secondary amines, a class of small molecules that are particularly important features of many pharmaceutical agents.
机译：基于未活化的C-H键催化功能化的新化学转化的发展具有极大简化复杂分子合成的潜力。过渡金属催化已成为将这些不活泼的键转化为碳-碳和碳-杂原子键的有力工具，但是脂族C-H键的选择性转化仍然是一个挑战。最成功的方法涉及一个“导向基团”，该基团将金属催化剂定位在特定的C-H键附近，从而使C-H官能化步骤通过环金属化进行。大多数定向的脂肪族C-H活化过程都是通过五元环的环金属化中间体进行的。考虑到由这些中间体引起的新反应的数量，似乎确定不同的环金属化途径可能会导致其他有用的化学转化的发展。在这里，我们报告钯催化的C H键激活模式通过四元环环钯途径进行。此处描述的化学作用导致与未保护的仲胺相邻的甲基选择性转化为合成用途的氮杂环。 CH动画和羰基化工艺的发展突显了这种先前未知的键断开的范围，从而导致了氮丙啶和β-内酰胺的合成，并暗示了通用的CH官能化平台可以简化脂肪族化合物的合成仲胺，一类小分子，在许多药物中特别重要。

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  • 来源
    《Nature》 |2014年第7503期|129-133|共5页
  • 作者

    Andrew McNally; Benjamin Haffemayer; Beatrice S. L. Collins; Matthew J. Gaunt;

  • 作者单位

    Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK;

    Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK;

    Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK;

    Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK;

  • 收录信息 美国《科学引文索引》(SCI);美国《工程索引》(EI);美国《生物学医学文摘》(MEDLINE);美国《化学文摘》(CA);
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  • 正文语种 eng
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