Mechanistically Guided Design of Ligands That Significantly Improve the Efficiency of CuH-Catalyzed Hydroamination Reactions.
Mechanistically Guided Design of Ligands That Significantly Improve the Efficiency of CuH-Catalyzed Hydroamination Reactions.
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在机械上引导的配体设计，可显着提高CuH催化的氢化反应的效率。
DOI：
10.1021/jacs.8b09565
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发表时间：
2018-10-24
影响因子：
15
通讯作者：
Buchwald SL
中科院分区：
文献类型：
--
作者：
Thomas AA;Speck K;Kevlishvili I;Lu Z;Liu P;Buchwald SL
使用机械引导的配体设计方法，一种新的配体（SEGFAST）的CuH催化的未活化的末端烯烃的氢胺化反应已经开发，提供了62倍的反应速率增加相比，DTBM-SEGPHOS，以前的最佳配体。结合计算化学和实验动力学测量的各自优势，我们能够快速识别导致更有效配体的潜在修饰，从而避免合成和测试大型配体库。通过优化有吸引力的非共价配体-底物相互作用和催化剂在反应条件下的稳定性的组合，我们能够鉴定出微调的杂化配体，其极大地使未活化的烯烃的铜氢化速率加快。此外，设计了一个模块化和强大的合成序列，这使得这些新的杂合配体结构的实用，克级合成。
Using a mechanistically guided ligand design approach, a new ligand (SEGFAST) for the CuH-catalyzed hydroamination reaction of unactivated terminal olefins has been developed, providing a 62-fold rate increase over reactions compared to DTBM-SEGPHOS, the previous optimal ligand. Combining the respective strengths of computational chemistry and experimental kinetic measurements, we were able to quickly identify potential modifications that lead to more effective ligands, thus avoiding synthesizing and testing a large library of ligands. By optimizing the combination of attractive, non-covalent ligand-substrate interactions and the stability of the catalyst under the reaction conditions, we were able to identify a finely-tuned hybrid ligand that greatly enables accelerated hydrocupration rates with unactivated alkenes. Moreover, a modular and robust synthetic sequence was devised, which allowed for practical, gram-scale synthesis of these novel hybrid ligand structures.
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