A new procedure for the oxidation of saturated hydrocarbons

Barton, Derek H. R.; Gastiger, Michel J.; Motherwell, William B.

doi:10.1039/c39830000041

Cited by 105 publications

(13 citation statements)

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“…[212] Ligands able to act as heme surrogates, such as pyridines and other cyclic amines, have attracted a great deal of attention. Early work on ironcatalyzed CÀH oxidations with these ligand types was carried out by the research groups of Tabushi [213] and Barton, [214,215] and more recently by Que and co-workers. [216] White and Chen have recently reported a highly selective iron(II) catalyst 237 capable of oxidizing tertiary C À H bonds in complex molecules.…”

Section: Metal-catalyzed C à H Activationmentioning

confidence: 99%

Chemoselectivity and the Curious Reactivity Preferences of Functional Groups

2009

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Achieving high levels of chemoselectivity has been the Achilles' heel of chemical synthesis. The excitement generated by the successful realization of chemoselective strategies underscores the painstaking efforts to define a set of conditions conducive to selection among the available reaction pathways. We discuss in this Review various aspects of chemoselectivity that have been addressed in a range of synthetic methods over the past decade. We have focused on the proposed mechanistic basis of the reactions under consideration in an attempt to categorize them and highlight the key concepts that have been emerging on the basis of these studies. Our overview of recent advances in chemoselective processes suggests that significant progress has been made, but a lot of challenges lie ahead.

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Section: Metal-catalyzed C à H Activationmentioning

confidence: 99%

Chemoselectivity and the Curious Reactivity Preferences of Functional Groups

2009

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“…The well-known propensity of adamantane (65) to undergo oxidation is an interesting peculiarity that has made it a yard-stick for CÀH activation, and numerous examples of its oxidation have been documented (Scheme 10). [84] The ease of oxidation of the tertiary bridgehead position of this substrate has resulted in a common misperception that the oxidation of bridgehead positions (C1) in general is a relatively simple task. The reduced selectivity observed for bicyclo[2.2.2]octane (66) [18] and the reversal of selectivity observed for bicyclo-[3.1.1]heptane [85] (67) and bicyclo[2.2.1]heptanes (not shown) [84a] illustrates the challenges associated with oxidizing bridgehead positions.…”

Section: Case Studiesmentioning

confidence: 99%

If CH Bonds Could Talk: Selective CH Bond Oxidation

2011

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C–H oxidation has a long history and an ongoing presence in research at the forefront of chemistry and interrelated fields. As such, numerous highly useful texts and reviews have been written on this subject. Logically, these are generally written from the perspective of the scope and limitations of the reagents employed. This minireview instead attempts to emphasize chemoselectivity imposed by the nature of the substrate. Consequently many landmark discoveries in the field of C–H oxidation are not discussed, but hopefully the perspective taken herein will allow for the more ready incorporation of C–H oxidation reactions into synthetic planning.

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“…Under these conditions, ketones and other byproducts were generated from one- and two-electron oxidations of cyclic alcohols . In the Gif oxygenation systems, these ferryl species are formed directly from O 2 in the presence of reductants (Zn or NaS) and pyridine. − While the culmination of this body of work has indeed yielded catalytic systems that can functionalize strong C–H bonds, many of these fundamentally important reactions suffer from unproductive oxidation and precipitation of the catalyst, a general lack of control over intermediary radical species, and limited regio- and stereoselectivity, hindering their applications more broadly.…”

Section: Nonheme Ironmentioning

confidence: 99%

Nature’s Machinery, Repurposed: Expanding the Repertoire of Iron-Dependent Oxygenases

2020

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Iron is an especially important redox-active cofactor in biology because of its ability to mediate reactions with atmospheric O 2 . Iron-dependent oxygenases exploit this earthabundant transition metal for the insertion of oxygen atoms into organic compounds. Throughout the astounding diversity of transformations catalyzed by these enzymes, the protein framework directs reactive intermediates toward the precise formation of products, which, in many cases, necessitates the cleavage of strong C-H bonds. In recent years, members of several iron-dependent oxygenase families have been engineered for new-to-nature transformations that offer advantages over conventional synthetic methods. In this Perspective, we first explore what is known about the reactivity of heme-dependent cytochrome P450 oxygenases and nonheme iron-dependent oxygenases bearing the 2-His-1-carboxylate facial triad by reviewing mechanistic studies with an emphasis on how the protein scaffold maximizes the catalytic potential of the iron-heme and iron cofactors. We then review how these cofactors have been repurposed for abiological transformations by engineering the protein frameworks of these enzymes. Finally, we discuss contemporary challenges associated with engineering these platforms and comment on their roles in biocatalysis moving forward.

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A new procedure for the oxidation of saturated hydrocarbons

Cited by 105 publications

References 1 publication

Chemoselectivity and the Curious Reactivity Preferences of Functional Groups

Chemoselectivity and the Curious Reactivity Preferences of Functional Groups

If CH Bonds Could Talk: Selective CH Bond Oxidation

Nature’s Machinery, Repurposed: Expanding the Repertoire of Iron-Dependent Oxygenases

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