当前位置: X-MOL 学术Nat. Catal. › 论文详情
Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)
A heterogeneous iridium single-atom-site catalyst for highly regioselective carbenoid O–H bond insertion
Nature Catalysis ( IF 37.8 ) Pub Date : 2021-06-21 , DOI: 10.1038/s41929-021-00637-7
Jie Zhao , Shufang Ji , Chenxi Guo , Haijing Li , Juncai Dong , Ping Guo , Dingsheng Wang , Yadong Li , F. Dean Toste

Transition-metal-catalysed carbenoid insertion of hydroxyl groups represents a robust and versatile method to forge C–O bonds. Achieving site-selective functionalization of alcohols using this transformation has undoubted synthetic value but remains challenging. Here we report a strategy for selective carbenoid O–H insertion that exploits an engineered heterogeneous iridium single-atom catalyst, thus providing opportunities for organic transformations by merging material science and catalysis. This catalytic protocol delivers excellent selectivities (up to 99:1) for the functionalization of aliphatic over phenolic O–H bonds, whereas the analogous homogeneous catalyst, Ir(ttp)COCl (ttp = 5,10,15,20-tetra-p-tolylporphyrinato), provided modest preferences. Density-functional-theory calculations suggest that the site-selectivity derives from the lower oxidation state of the iridium metal centre in the heterogeneous catalyst and its impact on the absorption energies of the reactants. These results showcase an example of a heterogeneous single-atom catalyst providing superior site-selectivity and provide a complementary strategy to address challenges in catalysis for organic synthesis.



中文翻译:

用于高区域选择性卡宾O-H键插入的非均相铱单原子位点催化剂

过渡金属催化的卡宾插入羟基代表了一种强大且通用的方法来形成 C-O 键。使用这种转化实现醇的位点选择性功能化无疑具有合成价值,但仍然具有挑战性。在这里,我们报告了一种选择性卡宾 O-H 插入策略,该策略利用工程化的非均相铱单原子催化剂,从而通过结合材料科学和催化为有机转化提供机会。该催化方案为脂肪族在酚 O-H 键上的官能化提供了出色的选择性(高达 99:1),而类似的均相催化剂 Ir(ttp)COCl (ttp = 5,10,15,20- tetrap-tolylporphyrinato),提供适度的偏好。密度泛函理论计算表明,位点选择性源于非均相催化剂中铱金属中心的较低氧化态及其对反应物吸收能的影响。这些结果展示了一个非均相单原子催化剂的例子,它提供了卓越的位点选择性,并提供了一种补充策略来应对有机合成催化中的挑战。

更新日期:2021-06-21
down
wechat
bug