Enantiotopos‐Selective CH Oxygenation Catalyzed by a Supramolecular Ruthenium Complex

Frost, James R.; Huber, Stefan M.; Breitenlechner, Stefan; Bannwarth, Christoph

doi:10.1002/anie.201409224

Cited by 110 publications

(58 citation statements)

References 59 publications

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“…As an initial solution, Bach and co-workers desymmetrized a spirocyclic oxindole to test their system ( Figure 64 a). 238 Following reaction completion, the crude mixture was exhaustively oxidized to convert any residual alcohol to the ketone. A slightly modified porphyrin catalyst was optimal and a representation of the proposed interactions involved in the transformation is shown below ( Figure 64 b).…”

Section: Carbon–heteroatom Bond-forming Reactionsmentioning

confidence: 99%

Recent Developments in Enantioselective Transition Metal Catalysis Featuring Attractive Noncovalent Interactions between Ligand and Substrate

et al. 2020

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Enantioselective transition metal catalysis is an area very much at the forefront of contemporary synthetic research. The development of processes that enable the efficient synthesis of enantiopure compounds is of unquestionable importance to chemists working within the many diverse fields of the central science. Traditional approaches to solving this challenge have typically relied on leveraging repulsive steric interactions between chiral ligands and substrates in order to raise the energy of one of the diastereomeric transition states over the other. By contrast, this Review examines an alternative tactic in which a set of attractive noncovalent interactions operating between transition metal ligands and substrates are used to control enantioselectivity. Examples where this creative approach has been successfully applied to render fundamental synthetic processes enantioselective are presented and discussed. In many of the cases examined, the ligand scaffold has been carefully designed to accommodate these attractive interactions, while in others, the importance of the critical interactions was only elucidated in subsequent computational and mechanistic studies. Through an exploration and discussion of recent reports encompassing a wide range of reaction classes, we hope to inspire synthetic chemists to continue to develop asymmetric transformations based on this powerful concept.

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Section: Carbon–heteroatom Bond-forming Reactionsmentioning

confidence: 99%

Recent Developments in Enantioselective Transition Metal Catalysis Featuring Attractive Noncovalent Interactions between Ligand and Substrate

et al. 2020

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“…As such, Bach’s group has disclosed highly enantiotopos-selective benzylic methylene oxidation of spirocyclic oxindole with a Ru-based catalyst structurally similar to 1 (ref. 34 ). With regard to nonactivated C( sp 3 )–H oxidation, Costas, Bietti, and coworkers have achieved highly enantiotopos-selective oxidation of amide-monosubstituted cyclohexane 35 .…”

Section: Introductionmentioning

confidence: 99%

Catalytic enantioselective C(sp3)–H functionalization involving radical intermediates

Zhang

et al. 2021

Nat Commun

114

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Recently, with the boosted development of radical chemistry, enantioselective functionalization of C(sp3)–H bonds via a radical pathway has witnessed a renaissance. In principle, two distinct catalytic modes, distinguished by the steps in which the stereochemistry is determined (the radical formation step or the radical functionalization step), can be devised. This Perspective discusses the state-of-the-art in the area of catalytic enantioselective C(sp3)–H functionalization involving radical intermediates as well as future challenges and opportunities.

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“… 9 Efforts have also been devoted to modify the innate relative reactivity of C–H bonds by introducing directing groups. 10 − 15 Alternatively, interaction of Lewis or Brønsted acids with amines builds up positive charge onto these groups and deactivates via polarity reversal the adjacent C–H bonds, directing oxidation to the most remote and less deactivated C–H bonds. 7 , 16 − 18 …”

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confidence: 99%

Chemoselective Aliphatic C–H Bond Oxidation Enabled by Polarity Reversal

et al. 2017

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Methods for selective oxidation of aliphatic C–H bonds are called on to revolutionize organic synthesis by providing novel and more efficient paths. Realization of this goal requires the discovery of mechanisms that can alter in a predictable manner the innate reactivity of these bonds. Ideally, these mechanisms need to make oxidation of aliphatic C–H bonds, which are recognized as relatively inert, compatible with the presence of electron rich functional groups that are highly susceptible to oxidation. Furthermore, predictable modification of the relative reactivity of different C–H bonds within a molecule would enable rapid diversification of the resulting oxidation products. Herein we show that by engaging in hydrogen bonding, fluorinated alcohols exert a polarity reversal on electron rich functional groups, directing iron and manganese catalyzed oxidation toward a priori stronger and unactivated C–H bonds. As a result, selective hydroxylation of methylenic sites in hydrocarbons and remote aliphatic C–H oxidation of otherwise sensitive alcohol, ether, amide, and amine substrates is achieved employing aqueous hydrogen peroxide as oxidant. Oxidations occur in a predictable manner, with outstanding levels of product chemoselectivity, preserving the first-formed hydroxylation product, thus representing an extremely valuable tool for synthetic planning and development.

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Enantiotopos‐Selective CH Oxygenation Catalyzed by a Supramolecular Ruthenium Complex

Cited by 110 publications

References 59 publications

Recent Developments in Enantioselective Transition Metal Catalysis Featuring Attractive Noncovalent Interactions between Ligand and Substrate

Recent Developments in Enantioselective Transition Metal Catalysis Featuring Attractive Noncovalent Interactions between Ligand and Substrate

Catalytic enantioselective C(sp3)–H functionalization involving radical intermediates

Chemoselective Aliphatic C–H Bond Oxidation Enabled by Polarity Reversal

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