Developing ligands for palladium(II)-catalyzed C-H functionalization: intimate dialogue between ligand and substrate.
Developing ligands for palladium(II)-catalyzed C-H functionalization: intimate dialogue between ligand and substrate.
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DOI：
10.1021/jo400159y
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发表时间：
2013-09-20
期刊：
影响因子：
--
通讯作者：
Yu JQ
中科院分区：
文献类型：
--
作者：
Engle KM;Yu JQ
均相过渡金属催化反应对于现代化学合成的各个方面都是不可或缺的。因此，很难想象在 20 世纪初的大部分时间里，所有已知的均相金属催化剂的反应活性和选择性与其非均相催化剂和生物催化剂相比都相形见绌。在接下来的几十年里，配体设计的进步弥合了这一鸿沟，使得今天一些最苛刻的成键事件是由配体支持的均质金属物质介导的。虽然配体设计推动了均相催化的许多领域，但在 Pd(II) 催化的 C-H 官能化领域，缺乏合适的配体支架，这阻碍了基于 C-H 官能化逻辑的广泛实用转化的发展。在这篇综述中，我们介绍了我们使用三种配体支架、单N-保护氨基酸、2,6-二取代吡啶和2,2'-联吡啶的研究，以解决几种合成多功能底物类别带来的挑战。利用这项工作，我们讨论了配体设计的原则，例如将配体与特定底物类别相匹配的需要，以及配体特征（例如可调性和模块化）如何在反应发现中发挥优势。
Homogeneous transition metal–catalyzed reactions are indispensable to all facets of modern chemical synthesis. It is thus difficult to imagine that for much of the early 20th century, the reactivity and selectivity of all known homogeneous metal catalysts paled in comparison to their heterogeneous and biological counterparts. In the intervening decades, advances in ligand design bridged this divide, such that today some of the most demanding bond-forming events are mediated by ligand-supported homogeneous metal species. While ligand design has propelled many areas of homogeneous catalysis, in the field of Pd(II)-catalyzed C–H functionalization, suitable ligand scaffolds are lacking, which has hampered the development of broadly practical transformations based on C–H functionalization logic. In this review, we offer an account of our research employing three ligand scaffolds, mono-N-protected amino acids, 2,6-disubstituted pyridines, and 2,2′-bipyridines, to address challenges posed by several synthetically versatile substrate classes. Drawing on this work, we discuss principles of ligand design, such as the need to match a ligand to a particular substrate class, and how ligand traits such as tunability and modularity can be advantageous in reaction discovery.
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影响因子：
15
作者：
Campbell AN;White PB;Guzei IA;Stahl SS
通讯作者：
Stahl SS
影响因子：
16.6
作者：
Chen, Xiao;Engle, Keary M.;Wang, Dong-Hui;Yu, Jin-Quan
通讯作者：
Yu, Jin-Quan
DOI：
10.1002/anie.198701901
发表时间：
1987-03-01
期刊：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION IN ENGLISH
影响因子：
--
作者：
BROWN, JM
通讯作者：
BROWN, JM
影响因子：
15
作者：
Baxter, Ryan D.;Sale, David;Blackmond, Donna G.
通讯作者：
Blackmond, Donna G.
影响因子：
15
作者：
Chen, Xiao;Hao, Xue-Shi;Yu, Jin-Quan
通讯作者：
Yu, Jin-Quan