On the road to stable, isolable [4]cumulenes: Reactivity and cyclization reactions
On the road to stable, isolable [4]cumulenes: Reactivity and cyclization reactions
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通往稳定、可分离的[4]积烯的道路：反应性和环化反应
DOI：
10.1002/poc.4454
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发表时间：
2022
影响因子：
1.8
通讯作者：
Tykwinski, Rik R.
中科院分区：
文献类型：
--
作者：
Johnson, Matthew A.;Meckes, Jakob A.;Bühringer, Martina U.;Zhou, Zheng;Kuwatani, Yoshiyuki;Ferguson, Michael J.;Wei, Zheng;Iyoda, Masahiko;Petrukhina, Marina A.;Tykwinski, Rik R.
报道了持久性四芳基[4]积木烯的设计和合成。含苯基端基的衍生物([4]PHAND[4]Ph/Ar*)在合成和/或提纯过程中容易发生反应，使目标产物的分离变得复杂，特别是分子间二聚反应。(3，5-二叔丁基)苯端基(Ar*)的引入提高了稳定性，最终得到稳定和可分离的[4]异丁烯[4]Ar*。然而，Cumulene[4]Ar*在加压条件下仍然容易发生二聚反应，而且在温和的条件下也很容易与亲电体反应，导致分子内环化。鉴于这些研究中副产物(化合物3、10、14、17、18)的结构复杂性，X射线结晶学在它们的鉴定中起着至关重要的作用。
The design and synthesis of persistent tetraaryl[4]cumulenes are reported. Derivatives with phenyl endgroups ([4]Phand[4]Ph/Ar*) are susceptible to reactions during synthesis and/or purification that complicate isolation of the desired product, particularly intermolecular dimerization reactions. Incorporation of (3,5‐di‐tert‐butyl)phenyl endgroups (Ar*) provides increased stability, culminating in the stable and isolable [4]cumulene[4]Ar*. Cumulene[4]Ar*remains, however, susceptible to dimerization under pressing conditions, and[4]Ar*also readily reacts with electrophiles under mild conditions that lead to intramolecular cyclization. Given the structural complexity of the side products in these studies (compounds3,10,14,17,18), X‐ray crystallography plays a vital role in their identification.