This Review summarizes the advancements in Pd-catalyzed C(sp3)–H activation via various redox manifolds, including Pd(0)/Pd(II), Pd(II)/Pd(IV), and Pd(II)/Pd(0). While few examples have been reported in the activation of alkane C–H bonds, many C(sp3)–H activation/C–C and C–heteroatom bond forming reactions have been developed by the use of directing group strategies to control regioselectivity and build structural patterns for synthetic chemistry. A number of mono- and bidentate ligands have also proven to be effective for accelerating C(sp3)–H activation directed by weakly coordinating auxiliaries, which provides great opportunities to control reactivity and selectivity (including enantioselectivity) in Pd-catalyzed C–H functionalization reactions.

/pdf/palladium-catalyzed-transformations-of-alkyl-c-h-bonds-4q9fij5w81.pdf

Palladium-Catalyzed Transformations of Alkyl C-H Bonds.

The present review is devoted to summarizing the recent advances (2015-2017) in the field of metal-catalysed group-directed C-H functionalisation In order to clearly showcase the molecular diversity that can now be accessed by means of directed C-H functionalisation, the whole is organized following the directing groups installed on a substrate Its aim is to be a comprehensive reference work, where a specific directing group can be easily found, together with the transformations which have been carried out with it Hence, the primary format of this review is schemes accompanied with a concise explanatory text, in which the directing groups are ordered in sections according to their chemical structure The schemes feature typical substrates used, the products obtained as well as the required reaction conditions Importantly, each example is commented on with respect to the most important positive features and drawbacks, on aspects such as selectivity, substrate scope, reaction conditions, directing group removal, and greenness The targeted readership are both experts in the field of C-H functionalisation chemistry (to provide a comprehensive overview of the progress made in the last years) and, even more so, all organic chemists who want to introduce the C-H functionalisation way of thinking for a design of straightforward, efficient and step-economic synthetic routes towards molecules of interest to them Accordingly, this review should be of particular interest also for scientists from industrial R&D sector Hence, the overall goal of this review is to promote the application of C-H functionalisation reactions outside the research groups dedicated to method development and establishing it as a valuable reaction archetype in contemporary R&D, comparable to the role cross-coupling reactions play to date

/pdf/a-comprehensive-overview-of-directing-groups-applied-in-543u6d0g60.pdf

A comprehensive overview of directing groups applied in metal-catalysed C-H functionalisation chemistry.

Despite being largely absent from natural products and biological processes, fluorine plays a conspicuous and increasingly important role within pharmaceuticals and agrochemicals, as well as in materials science.1a−1c Indeed, as many as 35% of agrochemicals and 20% of pharmaceuticals on the market contain fluorine.1d Fluorine is the most electronegative element in the periodic table, and the introduction of one or more fluorine atoms into a molecule can result in greatly perturbed properties. Fluorine substituents can potentially impact a number of variables, such as the acidity or basicity of neighboring groups, dipole moment, and properties such as lipophilicity, metabolic stability, and bioavailability. The multitude of effects that can arise from the introduction of fluorine in small molecules in the context of medicinal chemistry has been extensively discussed elsewhere.2

For these reasons, methods to introduce fluorine into small organic molecules have been actively investigated for many years by specialists in the field of fluorine chemistry. However, particularly in the past decade, a combination of the increasing importance of fluorine-containing molecules and the successful development of bench stable, commercially available fluorine sources has brought the expansion of fluorine chemistry into the mainstream organic synthesis community. This has resulted in an acceleration in the development of new fluorination methods and consequently in methods for the asymmetric introduction of fluorine.3 Catalytic asymmetric fluorination methods have inevitably lagged somewhat behind their nonasymmetric counterparts as understanding of the modes of reactivity of new fluorinating reagents must generally be developed and understood before they can be extended to enantioselective catalysis.3b Indeed, the last special issue of Chemical Reviews dedicated to fluorine chemistry, in 1996, contained no articles addressing asymmetric fluorine chemistry, and the editor of the issue noted that “although fluorine chemistry is much less abstruse now than when I entered the field a generation ago, it remains a specialized topic and most chemists are unfamiliar, or at least uncomfortable, with the synthesis and behavior of organofluorine compounds.”4 The field has undoubtedly undergone great change within the last two decades.

As with the incorporation of the fluorine atom, the introduction of the trifluoromethyl (CF3) group into organic molecules can substantially alter their properties. As with fluorine, the prevalence of CF3 groups in pharmaceuticals and agrochemicals coupled with the development of new trifluoromethylating reagents also has led to a recent surge in the development of asymmetric trifluoromethylation and perfluoroalkylation. Although the fluorine and trifluoromethyl moieties are often found on the aromatic rings of many pharmaceutical and agrochemicals rather than in aliphatic regions, this may be a result of the lack of efficient methods for the asymmetric introduction of C–F and C–CF3 bonds into molecules; it could be the case that lack of chemical methods is restricting useful exploration of such molecules. However, there are still encouraging examples of drug candidates containing chiral fluorine and trifluoromethyl-bearing carbons (Figure ​(Figure11).



Figure 1

Molecules of medicinal interest bearing C–F and C–CF3 stereocenters.

Advances in catalytic enantioselective fluorination, mono-, di-, and trifluoromethylation, and trifluoromethylthiolation reactions.

Fossils document the existence of trees and wood-associated organisms from almost 400 million years ago, and today there are between 400,000 and 1 million wood-inhabiting species in the world. This is the first book to synthesise the natural history and conservation needs of wood-inhabiting organisms. Presenting a thorough introduction to biodiversity in decaying wood, the book studies the rich diversity of fungi, insects and vertebrates that depend upon dead wood. It describes the functional diversity of these organisms and their specific habitat requirements in terms of host trees, decay phases, tree dimensions, microhabitats and the surrounding environment. Recognising the threats posed by timber extraction and forest management, the authors also present management options for protecting and maintaining the diversity of these species in forests as well as in agricultural landscapes and urban parks.

Biodiversity in dead wood.

Asymmetric Organocatalytic Cyclization and Cycloaddition Reactions

Aryl boronic acids can be monofluoromethylated under nickel catalysis. The utility of this method is demonstrated by the monofluoromethylation of a borylated and acyl-protected derivative of the statin drug ezetimibe. Mechanistic investigations indicate that a fluoromethyl radical is involved in the Ni(I)/Ni(III) catalytic cycle.

Nickel-catalyzed monofluoromethylation of aryl boronic acids.

Asymmetric Phase‐Transfer Catalysis

Highly efficient asymmetric amination of β-keto esters catalyzed by chiral quaternary ammonium bromides

Spiro-type phase-transfer catalysts prepared from two equivalents of a single binaphthyl subunit were designed and applied to the asymmetric alkylation and direct aldol reactions of a glycine derivative. The effects of the substitution pattern of the binaphthyl subunits on the enantioselectivity were also investigated.

Effects of Aromatic Substituents on Binaphthyl‐Based Chiral Spiro‐Type Ammonium Salts in Asymmetric Phase‐Transfer Reactions

The first example of palladium-catalyzed ortho-C–H arylation of aryl and benzyl Weinreb amides was developed, in which HOTf was used as a key promoter. This method exhibits good functional group tolerance, a broad substrate scope of both Weinreb amides and aryl iodides, high mono-selectivity and mild reaction conditions.

Pd(II)-catalyzed C-H arylation of aryl and benzyl Weinreb amides.

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