Iron Corrole‐Catalyzed Intramolecular Amination Reactions of Alkyl Azides. Spectroscopic Characterization and Reactivity of [Fe^V(Cor)(NAd)]

Advanced Science, Год журнала: 2024, Номер 11(39)

Опубликована: Авг. 20, 2024

Abstract As nitrogen analogues of iron‐oxo species, high‐valent iron‐imido species have attracted great interest in the past decades. Fe V ‐alkylimido are generally considered to be key reaction intermediates Fe(III)‐catalyzed C(sp 3 )─H bond aminations alkyl azides but remain underexplored. Here, it is reported that iron‐corrole (Cor) complexes can catalyze a wide range intramolecular C─H amination reactions afford variety 5‐, 6‐ and 7‐membered N‐heterocycles, including alkaloids natural product derivatives, with up 3880 turnover numbers (TONs) excellent diastereoselectivity (>99:1 d.r.). Mechanistic studies density functional theory (DFT) calculations intermolecular hydrogen atom abstraction (HAA) reveal reactive intermediates. The [Fe (Cor)(NAd)] (Ad = adamantyl) complex independently prepared characterized through electron paramagnetic resonance (EPR), Raman (rR) measurement, X‐ray photoelectron spectroscopy (XPS). This toward HAA kinetic isotope effects (KIEs) similar [Fe(Cor)]‐catalyzed azides.

Язык: Английский

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Skeletal Editing via Transition‐Metal‐Catalyzed Nitrene Insertion

The Chemical Record, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 28, 2024

Abstract Metal‐nitrenes are valuable reactive intermediates for synthesis and widely used to construct biologically relevant scaffolds, complexes functionalized molecules. The ring expansion of cyclic molecules via single‐nitrogen‐atom insertion nitrene or metal‐nitrenoid has emerged as a promising modern strategy driving advantageous nitrogen‐rich compound synthesis. In recent years, the catalytic single nitrogen atom into carbocycles, leading N‐heterocycles, become an important focus synthetic approaches with applications in medicinal chemistry, materials science, industry. Catalytic insertions have been increasing prominence organic due their capability high‐value added nitrogen‐containing heterocycles from simple feedstocks. this review, we will discuss rapidly growing field skeletal editing using transition metal catalysis access heterocycles, on across wide spectrum carbocycles.

Язык: Английский

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Highly Enantioselective Construction of Oxazolidinone Rings via Enzymatic C(sp³)–H Amination

ACS Catalysis, Год журнала: 2024, Номер unknown, С. 809 - 816

Опубликована: Дек. 27, 2024

Oxazolidinones are important heterocycles widely utilized in medicinal chemistry for the synthesis of antifungals, antibacterials, and other bioactive compounds organic as chiral auxiliaries asymmetric synthesis. Herein, we report a biocatalytic strategy enantioenriched oxazolidinones through intramolecular C(sp3)–H amination carbamate derivatives using engineered myoglobin-based catalysts. This method is applicable to diverse range substrates with high functional group tolerance provide good yields enantioselectivity. The synthetic utility this methodology further highlighted by development enantiodivergent biocatalysts transformation preparative-scale key oxazolidinone intermediates production cholesterol-lowering drugs ezetimibe CJ-15-161. An outer sphere mutation, Y146F, was found be beneficial favoring productive C–H reaction over an unproductive reductive pathway commonly observed hemeprotein-catalyzed nitrene transfer reactions. study demonstrates biocatalytic, via derivatives, which offers attractive these valuable applications chemistry, target-directed synthesis,

Язык: Английский

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A novel 5,10,15,20-tetrakis-(4-(triazol-1-yl)phenyl)porphyridine compound: Crystal structure, photophysical properties and TDDFT calculations

Journal of Porphyrins and Phthalocyanines, Год журнала: 2024, Номер 28(03), С. 157 - 165

Опубликована: Март 1, 2024

A novel 5,10,15,20-tetrakis-(4-(triazol-1-yl)phenyl)porphyridine compound, namely, Zn[5,10,15,20-tetrakis-(4-(triazol-1-yl)phenyl)porphyridine] (hereafter tagged as 1) was synthesized through a solvothermal reaction with mixed solvents at 413 K. The X-ray single-crystal structure of compound 1 is featured two-dimensional (2D) layer-like the zinc ion located center 5,10,15,20-tetrakis-(4-(triazol-1-yl)phenyl)porphyridine. macrocycle coplanar. has six coordination and coordinates three porphyridines. photoluminescence spectra DMF solution reveal that it shows upconversion red photoluminescence. time-dependent density functional theory (TDDFT) calculation confirms this originated from MLCT process (metal to ligand charge transfer). CCT (Correlated Color Temperature) 2200 K CIE (Commission Internationale de I’Éclairage) chromaticity coordinate (0.6311, 0.3595) for 1. UV-vis diffuse reflectance curve measured solid state sample reveals possesses 2.75 eV band gap.

Язык: Английский

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Enantioselective Nitrene Transfer to Hydrocinnamyl Alcohols and Allylic Alcohols Enabled by Systematic Exploration of the Structure of Ion-Paired Rhodium Catalysts

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(32), С. 22629 - 22641

Опубликована: Июль 31, 2024

This work describes highly enantioselective nitrene transfer to hydrocinnamyl alcohols (benzylic C–H amination) and allylic (aziridination) using ion-paired Rh (II,II) complexes based on anionic variants of Du Bois' esp ligand that are associated with cinchona alkaloid-derived chiral cations. Directed by a substrate hydroxyl group, our previous these had not been able achieve high enantioselectivity most useful short-chain compounds, we overcame this challenge through combination catalyst design modified conditions. A hypothesis modulation the linker between sulfonate group central arene spacer might provide better fit for shorter chain length substrates led development new biaryl-containing scaffold, which has allowed broad scope both classes be realized first time. Furthermore, describe systematic structural "knockout" study cation elucidate features crucial enantioinduction. De novo synthesis scaffolds surprising finding ee quinoline nitrogen alkaloid is crucial, although its location within heterocycle could varied, even leading superior catalyst. The free also should possess naturally occurring diastereomeric configuration alkaloid. These findings underline privileged nature scaffold insight into how cations used in other catalysis contexts.

Язык: Английский

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Enantioselective Intermolecular Benzylic C–H Amination under Chiral Paddle-Wheel Diruthenium Catalysis

ACS Catalysis, Год журнала: 2024, Номер 15(1), С. 523 - 528

Опубликована: Дек. 20, 2024

A catalytic asymmetric intermolecular benzylic C–H amination was achieved under paddle-wheel diruthenium catalysis. chiral catalyst incorporating (S)-TPPTTL (tetraphenylphthaloyl-(S)-tert-leucine) ligand exhibited notable enantioselectivity, and aminated products were obtained with up to 99% ee. Unique chemoselectivity of the also found for allylbenzene alkyl-naphthalene substrates, demonstrating complementary synthetic utility Ru(II)–Ru(III) catalysts Rh(II) counterparts.

Язык: Английский

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

Angewandte Chemie, Год журнала: 2024, Номер 136(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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Heme‐Enzymatic Biocatalysis for C−C or C−N Bond Formation

ChemCatChem, Год журнала: 2024, Номер 16(21)

Опубликована: Июль 15, 2024

Abstract The C−C or C−N bond formation is critical in the synthesis of pharmaceuticals and other value‐added products; however, traditional metal‐catalysed has brought about environmental resource issues. A plethora engineered heme‐dependent enzymes, such as cytochrome P450, have exhibited enormous potential biocatalysis for formation. With development computational spectroscopic methods, mechanisms underlying heme‐catalysed been extensively investigated. In presence carbene nitrene precursor, an active iron porphyrin ( IPC ) IPN formed, which subsequently reacts with a second substrate to form new bonds. Apart from widely studied / ‐facilitated catalytic pathway, halide‐initiated radical cyclization pathway Cpd‐I‐catalysed diradical also proposed. These mechanistic insights enabled rational engineering de novo design heme enzymes. This review summarises recent advances enzymatic presents successful applications mechanism‐based enzyme design. It would shed light on tailored biocatalysts complex but valuable industrial products.

Язык: Английский

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

Angewandte Chemie, Год журнала: 2024, Номер 136(34)

Опубликована: Май 2, 2024

Abstract 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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Transition‐Metal Catalyzed Enantioselective Aziridination Reaction: Recent Development in Catalysis and Future Perspectives

ChemCatChem, Год журнала: 2024, Номер 16(21)

Опубликована: Июль 16, 2024

Abstract Chiral aziridines are important motifs in natural products and biologically significant compounds, as well one of the most valuable versatile building blocks for construction diverse chiral functionalized amines. Because importance aziridines, various novel transition‐metal‐based catalytic systems synthetic strategies have been established to investigate highly effective enantioselective aziridination process. This review outlined recent advances made transition‐metal catalyzed reactions, challenges potential field at current stage.

Язык: Английский

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