Multiple C-H activations to construct biologically active molecules in a process completely free of organohalogen and organometallic components
Multiple C-H activations to construct biologically active molecules in a process completely free of organohalogen and organometallic components
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DOI：
10.1002/anie.200704092
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发表时间：
2008-01-01
影响因子：
16.6
通讯作者：
Shi, Zhang-Jie
中科院分区：
文献类型：
--
作者：
Li, Bi-He;Tian, Shi-Liang;Shi, Zhang-Jie
CHTOH功能化是构建复杂结构的最可持续和最直接的方法，在过去的几十年中受到了极大的关注。[1]通过直接的C3-H官能化，C3-C和C3-X键（X= B、N、O等）可以通过利用钌、铑、钯、铱和其它金属络合物作为催化剂的方法直接构建。[2]与活化sp3 C3 OH键相比，由于不饱和环形成许多天然产物、合成药物和材料中的主要骨架，因此已经进行了许多努力来活化sp2 C3 OH键，特别是芳香族键。[3]在各种活化芳环C1 H2键的方法中，Pd Ⅱ催化的亲电取代反应是最重要的方法之一。[4]尽管以前的研究，有效的方法来构建复杂的支架仍然是罕见的。[5]我们在此提出了一种新的途径，以接近高选择性的交叉偶联芳烃控制的导向基团。这种有效的方法适用于通过钯催化的多个C2 OH官能化在没有卤化物和有机金属试剂的情况下制备完全官能化的咔唑。一般的方法来构建联芳基通常使用过渡金属催化的偶联反应，其中芳烃被硼（或其他金属）和卤化物官能化。[6]最近的努力已经通过避免使用通过直接活化芳族C13 H键的偶联配偶体之一而使这种偶联更有效。[7]芳烃的同偶联
CÀH functionalization is the most sustainable and straightforward method to construct complicated structures and has received significant attention in the past several decades.[1] Through direct CÀH functionalization, CÀC and CÀX bonds (X= B, N, O, etc.) could be directly constructed by methods utilizing ruthenium, rhodium, palladium, iridium, and other metal complexes as catalysts.[2] Compared with the activation of sp3 CÀH bonds, many efforts have been made to activate sp2 CÀH bonds, especially aromatic ones, since unsaturated rings form the main scaffold in many natural products, synthetic drugs, and materials.[3] Among various methods to activate CÀH bonds of aromatic rings, PdII-catalyzed electrophilic substitution is one of the most important.[4] Despite previous research, efficient methods to construct complicated scaffolds are still rare.[5] We present herein a new pathway to approach highly selective cross-coupling of arenes controlled by directing groups. This effective method is applied to prepare fully functionalized carbazoles through PdII-catalyzed multiple CÀH functionalization in the absence of halides and organometallic reagents.General methods to construct biaryls typically use transition-metal-catalyzed coupling reactions in which the arenes are functionalized with boron (or other metals) and halides.[6] Recent efforts have made this coupling more efficient by avoiding the use of one of the coupling partners through direct activation of aromatic CÀH bonds.[7] Homocoupling of arenes