Discovery of an α-Amino C–H Arylation Reaction Using the Strategy of Accelerated Serendipity

McNally, Andrew; Prier, Christopher K.; MacMillan, David W. C.

doi:10.1126/science.1213920

Cited by 924 publications

(599 citation statements)

References 32 publications

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“…How do supramolecular chemists close this gap in complexity? Possible strategies include: 1) Copying Nature and using repetitive coupling chemistries to easily build different systems out of a family of building blocks (peptidomimetics); 43 2) Embracing robotic/automation for targeted syntheses and/or accelerated serendipity approaches 114 to host design; 3) Using fragment-based approaches and structurebased design. 115 Within the physical community, one ongoing debate involves the solvation of proteins and how this influences their properties.…”

Section: Recognition Mimicry and Interactions With Biomoleculesmentioning

confidence: 99%

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry

et al. 2017

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Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry. AbstractOn planet Earth, water is everywhere: the majority of the surface is covered with it; it is a key component of all life; its vapor and droplets fill the lower atmosphere; even rocks contain it and undergo geomorphological changes because of it. A community of physical scientists largely drives studies of the chemistry of water and aqueous solutions, with expertise in biochemistry, spectroscopy, and computer modeling. More recently however, supramolecular chemistry -with its expertise in macrocyclic synthesis and measuring supramolecular interactions -have renewed their interest in water-mediated non-covalent interactions. These two groups offer complementary expertise that, if harnessed, offers to accelerate our understanding of aqueous supramolecular chemistry and water writ large. This review summarizes the state-of-the-art of the two fields, and highlights where there is latent chemical space for collaborative exploration by the two groups. 4Water is ubiquitous and essential to life on planet Earth. A full understanding of aqueous solutions is therefore of significance to a wide range of fields within the atmospheric, environmental, biological and geological sciences. Within the chemical sciences, a deeper appreciation of how non-covalent interactions and chemical transformations are influenced by water would benefit a variety of fields. However, as we highlight here, there are many open questions regarding the chemical and physical properties of aqueous solutions.The aqueous realm is frequently bifurcated into the Hofmeister and hydrophobic effects, phenomena that respectively deal with the properties of solutions of salts and relatively nonpolar molecules. However, it is becoming increasingly evident that these areas do in fact frequently overlap; two prime examples being the accumulation of large polarizable anions at the air-water interface, 1-5 and the favorable interactions of polarizable anions with non-polar surfaces. [6][7][8][9][10][11][12][13][14][15] Thus the hydrophobic and Hofmeister effects are but part of a greater continuum of aqueous supramolecular chemistry, with many important and outstanding questions regarding the influence of the different kinds of non-covalent interactions involved.Studies of water and aqueous solutions have mostly been driven by the physical sciences community, a broad range of scientists whose expertise in spectroscopy, computer modeling, and biochemistry (to name just three areas) has generally not involved macrocycles or host molecules in general. However, for some time now, supramolecular chemists -with their expertise in macrocyclic synthesis and measuring weak non-covalent interactions -have been travelling a parallel course of exploration. This Review, inspired by discussions between sixteen members of each community at a recent workshop, 16 is an attempt to summarize what we know about aqueous solutions, what we do not know about them, and where the two communit...

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Section: Recognition Mimicry and Interactions With Biomoleculesmentioning

confidence: 99%

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry

et al. 2017

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“…[83][84][85][86][87][88] N,N-Dimethylanilines undergo addition onto electron-deficient alkenes 9 via α-amino radical intermediates and cyclization to give quinoline derivatives 10 (Scheme 31). MacMillian utilized nucleophilic α-amino radicals generated using visible light photoredox Ir(III) catalysis in substitutions onto electron-deficient dicyanobenzenes and heterocyclic variants, where the reductive loss of cyanide occurs (Scheme 33).…”

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confidence: 99%

“…MacMillian utilized nucleophilic α-amino radicals generated using visible light photoredox Ir(III) catalysis in substitutions onto electron-deficient dicyanobenzenes and heterocyclic variants, where the reductive loss of cyanide occurs (Scheme 33). 85,86 The α-amino radicals were also generated from α-amino acids via oxidative decarboxylation. 86 The choice of photocatalyst depends upon the required redox processes, and authors optimise the yield of the desired substitution product using several types of catalyst and conditions.…”

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confidence: 99%

A new era for homolytic aromatic substitution: replacing Bu₃SnH with efficient light-induced chain reactions

Gurry

Aldabbagh

2016

Org. Biomol. Chem.

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“…[7][8][9][10] Historically, photoredox catalysis focused mostly on transition metal complexes 11 and especially ruthenium and iridium polypyridyl complexes have been used and are the main representative photoredox catalysts. [12][13][14][15][16][17] However, organic dyes such as xanthene dyes fluorescein, eosin Y, eosin B, and rose bengal, represent another significant class of photocatalysts. [18][19][20][21] These compounds are metal-free and significantly less expensive but their further property tuning is very limited.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and properties of push-pull imidazole derivatives with application as photoredox catalysts

Hloukov¹,

Bure²

2017

Arkivoc

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Two new push-pull molecules with imidazole-4,5-dicarbonitrile acceptor, thiophene and 2-methoxythiophene donors with potential use in photoredox catalysis were designed and prepared. The synthesis started from commercially available imidazole-4,5-dicarbonitrile and its bromination and N-methylation. Subsequent Suzuki-Miyaura cross-coupling with (5-methoxy)thiophene-derived boronic acids afforded target push-pull derivatives. Beside common analytical methods, the molecular structure of 5-methoxythiophen-2-yl derivative has also been verified by X-ray analysis. DSC analyses showed remarkable thermal stabilities of both target derivatives with Tm and TD values above 150 and 270 °C, respectively. Fundamental properties and extent of the intramolecular charge-transfer were further studied by UV-VIS absorption spectra and DFT calculations. Fundamental photoredox properties of target imidazole derivatives were elucidated. Both push-pull molecules were preliminary tested as photoredox catalysts in cross-dehydrogenative coupling reaction between tetrahydroisoquinoline and nitromethane and the results were compared with those obtained by pyrazine-2,3-dicarbonitrile-derived catalyst.

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Discovery of an α-Amino C–H Arylation Reaction Using the Strategy of Accelerated Serendipity

Cited by 924 publications

References 32 publications

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry

A new era for homolytic aromatic substitution: replacing Bu₃SnH with efficient light-induced chain reactions

Synthesis and properties of push-pull imidazole derivatives with application as photoredox catalysts

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Discovery of an α-Amino C–H Arylation Reaction Using the Strategy of Accelerated Serendipity

Cited by 924 publications

References 32 publications

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry

Collaborative routes to clarifying the murky waters of aqueous supramolecular chemistry

A new era for homolytic aromatic substitution: replacing Bu3SnH with efficient light-induced chain reactions

Synthesis and properties of push-pull imidazole derivatives with application as photoredox catalysts

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A new era for homolytic aromatic substitution: replacing Bu₃SnH with efficient light-induced chain reactions