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Cleaving arene rings for acyclic alkenylnitrile synthesis
Nature ( IF 64.8 ) Pub Date : 2021-07-19 , DOI: 10.1038/s41586-021-03801-y
Xu Qiu 1 , Yueqian Sang 2 , Hao Wu 1, 3 , Xiao-Song Xue 2, 4 , Zixi Yan 1 , Yachong Wang 1 , Zengrui Cheng 1 , Xiaoyang Wang 1 , Hui Tan 1 , Song Song 1 , Guisheng Zhang 3 , Xiaohui Zhang 1 , K N Houk 4 , Ning Jiao 1, 5
Affiliation  

Synthetic chemistry is built around the formation of carbon–carbon bonds. However, the development of methods for selective carbon–carbon bond cleavage is a largely unmet challenge1,2,3,4,5,6. Such methods will have promising applications in synthesis, coal liquefaction, petroleum cracking, polymer degradation and biomass conversion. For example, aromatic rings are ubiquitous skeletal features in inert chemical feedstocks, but are inert to many reaction conditions owing to their aromaticity and low polarity. Over the past century, only a few methods under harsh conditions have achieved direct arene-ring modifications involving the cleavage of inert aromatic carbon–carbon bonds7,8, and arene-ring-cleavage reactions using stoichiometric transition-metal complexes or enzymes in bacteria are still limited9,10,11. Here we report a copper-catalysed selective arene-ring-opening reaction strategy. Our aerobic oxidative copper catalyst converts anilines, arylboronic acids, aryl azides, aryl halides, aryl triflates, aryl trimethylsiloxanes, aryl hydroxamic acids and aryl diazonium salts into alkenyl nitriles through selective carbon–carbon bond cleavage of arene rings. This chemistry was applied to the modification of polycyclic aromatics and the preparation of industrially important hexamethylenediamine and adipic acid derivatives. Several examples of the late-stage modification of complex molecules and fused ring compounds further support the potential broad utility of this methodology.



中文翻译:

用于无环烯基腈合成的芳烃环裂解

合成化学是围绕碳-碳键的形成而建立的。然而,选择性碳-碳键断裂方法的开发在很大程度上是一个尚未解决的挑战1,2,3,4,5,6。这些方法将在合成、煤液化、石油裂解、聚合物降解和生物质转化等方面具有广阔的应用前景。例如,芳环是惰性化学原料中普遍存在的骨架特征,但由于其芳香性和低极性,对许多反应条件呈惰性。在过去的一个世纪里,只有少数在恶劣条件下的方法实现了涉及惰性芳族碳-碳键断裂的直接芳烃环改性7,8,以及在细菌中使用化学计量的过渡金属配合物或酶的芳烃环裂解反应仍然有限9,10,11。在这里,我们报告了一种铜催化的选择性芳烃开环反应策略。我们的好氧氧化铜催化剂通过芳烃环的选择性碳-碳键断裂将苯胺、芳基硼酸、芳基叠氮化物、芳基卤化物、芳基三氟甲磺酸酯、芳基三甲基硅氧烷、芳基异羟肟酸和芳基重氮盐转化为烯基腈。该化学方法应用于多环芳烃的改性以及工业上重要的六亚甲基二胺和己二酸衍生物的制备。复杂分子和稠环化合物的后期修饰的几个例子进一步支持了这种方法的潜在广泛用途。

更新日期:2021-07-19
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