Recent developments in natural product synthesis using metal-catalysed C–H bond functionalisation

McMurray, Lindsay; O’Hara, Fionn; Gaunt, Matthew J.

doi:10.1039/c1cs15013h

Cited by 1,540 publications

(237 citation statements)

References 112 publications

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“…7,8,174–180 Furthermore, aliphatic C–H bonds are one of the least reactive functional groups in organic chemistry, as their stability to most reaction conditions has informed the strategies of chemical synthesis, in targeting more traditionally reactive chemical handles, for centuries. 177 Hence, it is a substantial challenge to override a reagent’s or catalyst’s propensity to react with customarily more activated functional groups, such as alkenes, alcohols, or carbonyls, in order to achieve C–H bond functionalizations. Moreover, owing to their low polarity, most C–H bonds are chemically similar, which requires catalysts to differentiate between extremely subtle electronic and steric variations among a myriad of comparable bonds.…”

Section: C–h Oxidationmentioning

confidence: 99%

Applications of Nonenzymatic Catalysts to the Alteration of Natural Products

2017

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The application of small molecules as catalysts for the diversification of natural product scaffolds is reviewed. Specifically, principles that relate to the selectivity challenges intrinsic to complex molecular scaffolds are summarized. The synthesis of analogs of natural products by this approach is then described as a quintessential “late-stage functionalization” exercise wherein natural products serve as the lead scaffolds. Given the historical application of enzymatic catalysts to the site-selective alteration of complex molecules, the focus of this review is on the recent studies of non-enzymatic catalysts. Reactions involving hydroxyl group derivatization with a variety of electrophilic reagents are discussed. C–H bond functionalizations that lead to oxidations, aminations, and halogenations are also presented. Several examples of site-selective olefin functionalizations and C–C bond formations are also included. Numerous classes of natural products have been subjected to these studies of site-selective alteration including polyketides, glycopeptides, terpenoids, macrolides, alkaloids, carbohydrates and others. What emerges is a platform for chemical remodeling of naturally occurring scaffolds that targets virtually all known chemical functionalities and microenvironments. However, challenges for the design of very broad classes of catalysts, with even broader selectivity demands (e.g., stereoselectivity, functional group selectivity, and site-selectivity) persist. Yet, a significant spectrum of powerful, catalytic alterations of complex natural products now exists such that expansion of scope seems inevitable. Several instances of biological activity assays of remodeled natural product derivatives are also presented. These reports may foreshadow further interdisciplinary impacts for catalytic remodeling of natural products, including contributions to SAR development, mode of action studies, and eventually medicinal chemistry.

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Section: C–h Oxidationmentioning

confidence: 99%

Applications of Nonenzymatic Catalysts to the Alteration of Natural Products

2017

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“…[1][2][3][4][5][6][7] A relatively inert C-H bond is activated, and the hydrogen atom acts essentially as a leaving group. This technology allows one to bypass the installation and subsequent removal of classical leaving groups and to reduce wastes as well as some precautions (such as protecting group manipulations) typical in the handling of promiscuous amine reagents.…”

Section: Introductionmentioning

confidence: 99%

Recent advances on nickel-catalyzed C–H bonds functionalized reactions

Cai¹,

Xie²

2015

Arkivoc

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The direct C-H bond functionalization has been one of the most active research fields in organic chemistry not only due to the significance in basic studies of inert C-H bond chemistry but also due to the step economy feature in potential synthetic application. In the past decades, transition-metalcatalyzed direct and selective functionalization of C-H bonds has emerged as a straightforward and environmentally friendly synthetic tool, which is also a long-standing goal that continues to drive discovery in organic synthesis. The precious late transition metals have been proved to play key roles to facilitate highly efficient transformations through C-H functionalization. However, the relatively high price, low natural abundance and partly strong toxicity limited their application. Nickel, compared to precious transition metals, is showing great potential for C-H bond functionalizations because of its low cost, unique reactivity profiles and easy availability in the earth's crust. This tutorial review summarizes the recent advances in nickel-mediated direct C-H bond functionalizations and C−C bond forming reactions.

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“…In the last years, selective catalytic oxidations of unactivated C-H bonds have attracted great attention: this approach, if implemented on preparative scale, could provide easy and efficient methodologies for the directed introduction of oxygen atom into complex organic molecules at late stages of multistep syntheses, on the basis of novel synthetic strategies [1][2][3][4][5][6][7][8][9][10][11]. Selective C-H oxidation reactions may lead to formation of new C-C and C-X (e.g., C-O, C-N, C-S, C-halogen, etc.…”

Section: Introductionmentioning

confidence: 99%

Direct Selective Oxidative Functionalization of C–H Bonds with H2O2: Mn-Aminopyridine Complexes Challenge the Dominance of Non-Heme Fe Catalysts

2016

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Non-heme iron(II) complexes are widespread synthetic enzyme models, capable of conducting selective C-H oxidation with H 2 O 2 in the presence of carboxylic acid additives. In the last years, structurally similar manganese(II) complexes have been shown to catalyze C-H oxidation with similarly high selectivity, and with much higher efficiency. In this mini-review, recent catalytic and mechanistic data on the selective C-H oxygenations with H 2 O 2 in the presence of manganese complexes are overviewed. A distinctive feature of catalyst systems of the type Mn complex/H 2 O 2 /carboxylic is the existence of two alternative reaction pathways (as found for the oxidation of cumenes), one leading to the formation of alcohol, and the other to ester. The mechanisms of formation of the alcohol and the ester are briefly discussed.

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Recent developments in natural product synthesis using metal-catalysed C–H bond functionalisation

Cited by 1,540 publications

References 112 publications

Applications of Nonenzymatic Catalysts to the Alteration of Natural Products

Applications of Nonenzymatic Catalysts to the Alteration of Natural Products

Recent advances on nickel-catalyzed C–H bonds functionalized reactions

Direct Selective Oxidative Functionalization of C–H Bonds with H2O2: Mn-Aminopyridine Complexes Challenge the Dominance of Non-Heme Fe Catalysts

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