Dual Chalcogen-Chalcogen Bonding Catalysis
Dual Chalcogen-Chalcogen Bonding Catalysis
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双硫族元素-硫族元素键合催化
DOI：
10.1021/jacs.9b12610
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发表时间：
2020
影响因子：
15
通讯作者：
Wang Yao
中科院分区：
文献类型：
--
作者：
Wang Wei;Zhu Haofu;Feng Lei;Yu Qun;Hao Jingcheng;Zhu Rongxiu;Wang Yao
非共价的S···O键相互作用是一种进化的力量，大自然巧妙地利用它来调节蛋白质的构象偏好。利用这种弱的非共价力来驱动化学反应是有希望的，但在很大程度上仍然难以捉摸。在这里，我们描述了一种双重硫族-硫族成键催化策略，即不同的硫族原子同时与两个基于硫族的电子给体相互作用，从而提高催化活性，从而促进化学反应。传统的Rauhut-Currier型反应方法需要使用强亲核的Lewis碱作为基本的促进剂。这种双重硫族-硫族键合催化策略的实施允许硫族键合供体与烯酮和醇之间同时进行Se···O键相互作用，从而能够以不同的方式实现Rauhut-Currier类型的反应。连续的双Se···O键催化方法的进一步实施使初始的Rauhut-Currier型反应得以实现，从而得到了烯酮产物，该产物进一步经历了醇加成诱导的环化反应。这项工作表明，近线性的硫基键相互作用可以区分相似的烷基，从而产生区域选择性。此外，新的策略显示了它的优势，因为它不仅使活性较低的基质能够有效地工作，而且可以容忍使用传统方法无法接触到的基质。
The noncovalent S···O bonding interaction is an evolutionary force that has been smartly exploited by nature to modulate the conformational preferences of proteins. The employment of this type of weak noncovalent force to drive chemical reactions is promising yet remains largely elusive. Herein, we describe a dual chalcogen–chalcogen bonding catalysis strategy that the distinct chalcogen atoms simultaneously interact with two chalcogen-based electron donors to give rise to the catalytic activity, thus facilitating chemical reactions. Conventional approaches to the Rauhut–Currier-type reactions require the use of strongly nucleophilic Lewis bases as essential promoters. The implementation of this dual chalcogen–chalcogen bonding catalysis strategy allows the simultaneous Se···O bonding interaction between chalcogen-bonding donors and an enone and an alcohol, enabling the realization of the Rauhut–Currier-type reactions in a distinct way. The further implementation of a consecutive dual Se···O bonding catalysis approach enables the achievement of an initial Rauhut–Currier-type reaction to give an enone product which further undergoes an alcohol-addition induced cyclization reaction. This work demonstrates that the nearly linear chalcogen-bonding interaction can differentiate similar alkyl groups to give rise to regioselectivity. Moreover, the new strategy shows its advantage as it not only enables less reactive substrates working efficiently but tolerates inaccessible substrates using conventional methods.