Site-selective functionalization of remote aliphatic C–H bonds <i>via</i> C–H metallation

Zhang, Qi; Shi, Bing‐Feng

doi:10.1039/d0sc05944g

Cited by 85 publications

(39 citation statements)

References 87 publications

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“…Remote C(sp 3 )-H bond functionalization chemistry (Qiu and Wu, 2015;Sharma, 2018) has progressed slowly compared to the activation and subsequent transformation of remote C(sp 2 )-H bonds (see: Ali and Siddiqui, 2021;Genov et al, 2020;Lu et al, 2019;Kuninobu et al, 2015). In particular, asymmetric functionalization of remote C(sp 3 )-H bonds in easily accessible organic molecules remains underdeveloped, presumably due to the entropic penalty for the formation of larger-membered metallacycles via C-H metalation (Zhang and Shi, 2021). In this context, the functionalization was limited to specific substrates that do not have the conventional accessible C-H bonds to effect remote directing.…”

Section: Asymmetric Borylation Of C(sp 3 )-H Bondsmentioning

confidence: 99%

An Introductory Overview of C–H Bond Activation/ Functionalization Chemistry with Focus on Catalytic C(sp3)–H Bond Borylation

Reyes

Sawamura

2021

KIMIKA

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The direct and selective functionalization of C–H bonds provides novel disconnections and innovative strategies to streamline the synthesis of molecules with diverse complexities. However, despite the significant advances in the elaboration of techniques for C–H activation, the utilization of unactivated C(sp3)–H bonds remains challenging. In particular, asymmetric transformation of C(sp3)–H bonds is underdeveloped owing to the lack of catalytic systems that can competently discriminate among ubiquitous C–H bonds in organic molecules. This short review aims to outline the challenges and strategies for the catalytic functionalization of C(sp3)–H bonds giving a general and non-exhaustive explanatory approach. Current strategies on the basis of the substrates and reaction mechanisms are summarized in Section 1. Examples of enantioselective C–H bond transformations are then given in Section 2. Finally, in Section 3, an outline of current methodologies towards the direct borylation of C(sp3)–H bonds is described to showcase the importance of developing techniques for catalytic C–H bond chemistry. While we try to cover all excellent reports available in the literature on this topic, any omissions are unintentional, taking note of the most representative examples available.

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Section: Asymmetric Borylation Of C(sp 3 )-H Bondsmentioning

confidence: 99%

An Introductory Overview of C–H Bond Activation/ Functionalization Chemistry with Focus on Catalytic C(sp3)–H Bond Borylation

Reyes

Sawamura

2021

KIMIKA

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“…随后, 该课题组又进一步拓宽到非联芳类底物, 用于吲哚啉 [66] 和吲哚类 [67] 化合物的合成. 2018 年, 该课题组 [68] [69] , 目前铜催化 C(sp 3 )-H 胺化反应仅有几例报道. 2014 年, Kanai 课题组 [70] (Scheme 26, a)和葛海波(Scheme 26, b)课题组 [71] 报道了 8-氨基喹啉导向的铜催化 C(sp 3 )-H 内酰胺化反应, 实现了 β-内酰胺的高效构建 [72] .…”

Section: 以羟胺及其衍生物为胺化试剂unclassified

Recent Advances in Base Metal (Copper, Cobalt and Nickel)-Catalyzed Directed C—H Amination

Feng¹,

Shi²

2021

Chinese Journal of Organic Chemistry

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Nitrogen-containing organic compounds are ubiquitous in natural products, drug molecules and organic intermediates. Therefore, the introduction of nitrogenous functional groups into organic compounds is of great significance. Despite transition metalcatalyzed C-N coupling reaction provided an effcient strategy to access these ntrogen-containing compounds, extra steps are generally required to obtain the pre-functionalized starting materials. Recently, transi-tionmetalcatalyzed C-H amination has emerged as a more atom-and step-economical strategy to construct C-N bonds. Compared to the noble metals (e.g. palladium and rhodium), base metal catalysts, such as copper, cobalt and nickel, have attracted dramatic attentions, due to their earth abundance, cost effectiveness, and unique catalytic activities. Herein, the recent advances in copper-, cobalt-and nickel-catalyzed C-H amination reactions assisted by directing groups were summmarized according to the types of base metals, C-H bonds, and amination reagents with an emphasis on the discussion of various amination reagents and their application. Finally, the limitations and development trend of this research field are analyzed and prospected.

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“…In the chemical industry, it is important that the properly activated catalyst not only has high selectivity, but also shows precise and controlled reactivity. Moreover, in accordance with the principles of "green chemistry" the generated waste should be as little environmentally harmful as possible [ 75 , 76 ]. The use of eco-friendly oxidants like dioxygen or hydrogen peroxide in broadly understood oxidation reactions is a subject of continued attention.…”

Section: N -Pentadentate Iron and Manganese Complexes – Recent Trends In Catalysismentioning

confidence: 99%

The most reactive iron and manganese complexes with N-pentadentate ligands for dioxygen activation—synthesis, characteristics, applications

Rydel-Ciszek

2021

Reac Kinet Mech Cat

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The iron and manganese complexes that activate oxygen atom play multiple role in technologically relevant reactions as well as in biological transformations, in which exist in different redox states. Among them, high-valent oxo intermediate seems to be the most important one. Iron, and/or manganese-based processes have found application in many areas, starting from catalysis and sustainable technologies, through DNA oxidative cleavage, to new substances useful in chemotherapeutic drugs. This review is not only the latest detailed list of uses of homogeneous N-pentadentate iron and manganese catalysts for syntheses of valuable molecules with huge applications in green technologies, but also a kind of "a cookbook", collecting "recipes" for the discussed complexes, in which the sources necessary to obtain a full characterization of the compounds are presented. Following the catalytic activity of metalloenzymes, and taking into account the ubiquity of iron and manganese salts, which in combination with properly designed ligands may show similarity to natural systems, the discussed complexes can find application as new anti-cancer drugs. Also, owing to ability of oxygen atom to exchange in reaction with H2O, they can be successfully applied in photodriven reactions of water oxidation, as well as in chemically regenerated fuel cells as a redox catalyst. Graphical abstract

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Site-selective functionalization of remote aliphatic C–H bonds via C–H metallation

Abstract: Recent advances in site-selective functionalization of remote aliphatic C–H bonds in organometallic pathways are summarized.

Cited by 85 publications

References 87 publications

An Introductory Overview of C–H Bond Activation/ Functionalization Chemistry with Focus on Catalytic C(sp3)–H Bond Borylation

An Introductory Overview of C–H Bond Activation/ Functionalization Chemistry with Focus on Catalytic C(sp3)–H Bond Borylation

Recent Advances in Base Metal (Copper, Cobalt and Nickel)-Catalyzed Directed C—H Amination

The most reactive iron and manganese complexes with N-pentadentate ligands for dioxygen activation—synthesis, characteristics, applications

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