The great strides of iron photosensitizers for contemporary organic photoredox catalysis: On our way to the holy grail?

Coordination Chemistry Reviews, Год журнала: 2023, Номер 500, С. 215522 - 215522

Опубликована: Ноя. 9, 2023

Язык: Английский

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Catalytic, asymmetric carbon–nitrogen bond formation using metal nitrenoids: from metal–ligand complexes via metalloporphyrins to enzymes

Chemical Science, Год журнала: 2023, Номер 14(44), С. 12447 - 12476

Опубликована: Янв. 1, 2023

The introduction of nitrogen atoms into small molecules is fundamental importance and it vital that ever more efficient selective methods for achieving this are developed. With aim, the potential nitrene chemistry has long been appreciated but its application constrained by extreme reactivity these labile species. This liability however can be attenuated complexation with a transition metal resulting nitrenoids have unique highly versatile which includes amination certain types aliphatic C-H bonds as well reactions alkenes to afford aziridines. At least one new chiral centre typically formed in processes development catalysts exert control over enantioselectivity nitrenoid-mediated become growing area research, particularly past two decades. Compared some synthetic methods, nitrenoid notable chemists draw from diverse array metals , ranging metal-ligand complexes, bearing variety ligand types, via bio-inspired metalloporphyrins, all way through to, very recently, engineered enzymes themselves. In latter category particular, rapid progress being made, rate suggests approach may instrumental addressing outstanding challenges field. review covers key developments strategies shaped field, addition latest advances, up until September 2023.

Язык: Английский

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Intermolecular Enantioselective Amination Reactions Mediated by Visible Light and a Chiral Iron Porphyrin Complex

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(34)

Опубликована: Май 2, 2024

In the presence of 1 mol % a chiral iron porphyrin catalyst, various 3-arylmethyl-substituted 2-quinolones and 2-pyridones underwent an enantioselective amination reaction (20 examples; 93-99 ee). The substrates were used as limiting reagents, fluorinated aryl azides (1.5 equivalents) served nitrene precursors. is triggered by visible light which allows facile dediazotation at ambient temperature. selectivity governed two-point hydrogen bond interaction between ligand catalyst substrate. Hydrogen bonding directs to specific atom within substrate that displaced nitrogen substituent either in concerted fashion or rebound mechanism.

Язык: Английский

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Tertiary Amides as Directing Groups for Enantioselective C−H Amination using Ion‐Paired Rhodium Complexes

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(14)

Опубликована: Фев. 13, 2024

Abstract Enantioselective C−H amination at a benzylic methylene is vital disconnection towards chiral benzylamines. Here we disclose that butyric and valeric acid‐derived tertiary amides can undergo highly enantioselective using an achiral anionic Rh complex ion‐paired with Cinchona alkaloid‐derived cation. A broad scope of compounds be aminated encompassing numerous arene substitutions, amides, two different chain lengths. Excellent tolerance ortho substituents was observed, which has not been achieved before in asymmetric intermolecular Rh. We speculate the amide group substrate engages hydrogen bonding interactions directly cation, enabling high level organisation transition state for amination. This contrast our previous work where bearing bond donor required. Control experiments led to discovery methyl ethers also function as proficient directing groups under optimised conditions, potentially acting acceptors. finding promise dramatically expand applicability catalysts.

Язык: Английский

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Asymmetric Intramolecular Amination Catalyzed with Cp*Ir-SPDO via Nitrene Transfer for Synthesis of Spiro-Quaternary Indolinone

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 18841 - 18847

Опубликована: Июль 8, 2024

An asymmetric intramolecular spiro-amination to high steric hindering

Язык: Английский

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Design and Synthesis of C₄‐Symmetric Axially Chiral β‐Aryl Porphyrins and Application for Supporting Ir(III)‐Catalyzed Enantioselective C−H Alkylation

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(28)

Опубликована: Апрель 29, 2024

A hitherto unknown class of C

Язык: Английский

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Organo‐Photocatalytic Anti‐Markovnikov Hydroamidation of Alkenes with Sulfonyl Azides: A Combined Experimental and Computational Study

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(26)

Опубликована: Апрель 17, 2024

The construction of C(sp

Язык: Английский

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Iron-catalysed stereoselective NH transfer enables dynamic kinetic resolution of sulfoxides

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Фев. 8, 2025

Transition metal-catalysed asymmetric nitrene transfer provides a powerful means to access various bioactive N-containing compounds as single enantiomers. However, enantioselective NH that allows concise assembly of unprotected enantioenriched amines remains an enduring challenge. We report here iron-catalysed stereoselective imidation sulfoxide, which is integrated with photocatalytic racemisation enabling dynamic kinetic resolution (DKR) strategy for direct and synthesis NH-sulfoximines. This approach distinct from the existing methods by avoiding protecting group manipulations and/or use chiral substrates. Computational studies on reaction suggest involvement iron-aminyl radical intermediate, its sulfoxide proceeds through synchronous nucleophilic addition nitrogen center ligand-to-metal electron process form N–S bond. In addition, stereoselectivity primarily dictated difference in dispersion interactions transition states. Enantioselective Here, authors

Язык: Английский

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Mechanistic and Computational Insights into Asymmetric Intramolecular Iron-Catalyzed Nitrene Transfer into Benzylic C–H Bonds

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 3789 - 3798

Опубликована: Фев. 18, 2025

Язык: Английский

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Designing Ruthenium Phthalocyanine with Chiral Pockets Formed by (1R,2S,5R)-Menthoxy Groups for Enantioselective Catalysis

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4984 - 5001

Опубликована: Март 10, 2025

Unprecedented chiral ruthenium(II) complexes with phthalocyanines having motifs near the catalytic metal site have been prepared by cross condensation of 3,6-bis-aryloxy-phthalonitrile (α-Ar*O)2Pn bearing two (1R,2S,5R)-menthoxy groups orthogonal to aromatic plane and (15-crown-5)phthalonitrile. Four containing menthyl (M) 15-crown-5 units (C), notably RuPc[MC3](CO), RuPc[opp-M2C2](CO), RuPc[adj-M2C2](CO), RuPc[M3C](CO), were isolated in pure form fully characterized UV–vis, circular dichroism, HRMS, various 1H NMR 13C techniques. Their evaluation benchmark asymmetric cyclopropanation reaction styrene derivatives ethyl diazoacetate indicated that RuPc[opp-M2C2](CO) complex was most efficient terms diastereo- enantioselectivity. Further study revealed strong dependence stereoselectivity on solvent nature salt additives, which caused conformational rearrangement flexible surrounding, as evidenced multinuclear CD spectra. For instance, upon moving from commonly used CH2Cl2 EtOH addition NaPF6, a significant enhancement enantioselectivity (from 35 84% p-methylstyrene) obtained. Of particular importance is very high diastereoselectivity many substrates promoted incorporation sodium cations into crown ether cavities phthalocyanine attain trans/cis ratio up 499:1. Such regulating effect catalysis involving tetrapyrrolic has not previously observed, rendering this prominent example tunable catalyst. The developed synthetic strategy paves way environment around receptors tune properties.

Язык: Английский

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