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

Chemical Science, Journal Year: 2023, Volume and Issue: 14(44), P. 12447 - 12476

Published: Jan. 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.

Language: Английский

---

Copper/BINOL-Catalyzed Enantioselective C–H Functionalization toward Planar Chiral Ferrocenes Under Mild Conditions

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 4030 - 4039

Published: Feb. 28, 2024

Copper-catalyzed enantioselective C–H activation proceeding through an inner-sphere mechanism remains a huge challenge. Herein, copper-catalyzed alkynylation with terminal alkynes assisted by 8-aminoquinoline using readily available (S)-BINOL as the chiral ligand was disclosed. The reaction proceeded under mild conditions catalytic amount of copper salt, providing range ferrocenes in good yields and enantioselectivities (0 °C, up to 77% yield 94% ee). alteration stoichiometric chemical oxidant renewable electricity is also feasible at ambient temperature, demonstrating robustness this copper/BINOL catalysis. Notably, first cupraelectrocatalyzed reaction. Gram-scale synthesis, versatile transformations, application resulting oxazoline–olefin asymmetric synthesis highlight utility protocols.

Language: Английский

---

Strategies and Mechanisms of First-Row Transition Metal-Regulated Radical C–H Functionalization

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(17), P. 10192 - 10280

Published: Aug. 8, 2024

Radical C–H functionalization represents a useful means of streamlining synthetic routes by avoiding substrate preactivation and allowing access to target molecules in fewer steps. The first-row transition metals (Ti, V, Cr, Mn, Fe, Co, Ni, Cu) are Earth-abundant can be employed regulate radical functionalization. use such is desirable because the diverse interaction modes between metal complexes species including addition center, ligand complexes, substitution single-electron transfer radicals hydrogen atom noncovalent complexes. Such interactions could improve reactivity, diversity, selectivity transformations allow for more challenging reactions. This review examines achievements this promising area over past decade, with focus on state-of-the-art while also discussing existing limitations enormous potential high-value regulated these metals. aim provide reader detailed account strategies mechanisms associated

Language: Английский

---

Iron-Catalyzed Asymmetric Imidation of Sulfides via Sterically Biased Nitrene Transfer

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(26), P. 18050 - 18060

Published: June 15, 2024

Transition-metal-catalyzed enantioselective nitrene transfer to sulfides has emerged as one of the most powerful strategies for rapid construction enantioenriched sulfimides. However, achieving stereocontrol over highly active earth-abundant transition-metal nitrenoid intermediates remains a formidable challenge compared with precious metals. Herein, we disclose chiral iron(II)/N,N′-dioxide-catalyzed imidation dialkyl and alkyl aryl using iminoiodinanes precursors. A series sulfimides were obtained in moderate-to-good yields high enantioselectivities (56 examples, up 99% yield, 98:2 e.r.). The utility this methodology was demonstrated by late-stage modification complex molecules synthesis insecticide sulfoxaflor related bioactive compounds. Based on experimental studies theoretical calculations, water-bonded high-spin iron species identified key intermediate. observed stereoselectivity original from steric repulsion between amide unit ligand cave bulky substituent sulfides. Additionally, dioxazolones proved be suitable acylnitrene precursors presence an iron(III)/N,N′-dioxide complex, resulting formation enantioselectivity-reversed (14 81% 97:3

Language: Английский

---

Iridium-Catalyzed Migratory Terminal C(sp³)–H Amidation of Heteroatom-Substituted Internal Alkenes via Olefin Chain Walking

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: unknown

Published: Oct. 31, 2023

Hydroamination facilitated by metal hydride catalysis is an appealing synthetic approach to access valuable nitrogen-containing compounds from readily available unsaturated hydrocarbons. While high regioselectivity can be achieved usually for substrates bearing polar chelation groups, the reaction involving simple alkenes frequently provides nonselective outcomes. Herein, we report iridium-catalyzed highly regioselective terminal C(sp3)-H amidation of internal utilizing dioxazolones as amino source via olefin chain walking. Most notably, this mechanistic motif double bond migration position operates not only with dialkyl-substituted including styrenes but also heteroatom-substituted olefins such enol ethers, vinyl silanes, and borons, thus representing first example methyl latter type through a nondissociative walking process.

Language: Английский

---

Photochemical Deracemization of Lactams with Deuteration Enabled by Dual Hydrogen Atom Transfer

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 18, 2024

Photochemical deracemization has emerged as one of the most straightforward approaches to access highly enantioenriched compounds in recent years. While excited-state events such energy transfer, single electron and ligand-to-metal charge transfer have been leveraged promote stereoablation, relying on hydrogen atom which circumvent limitations imposed by triplet redox potential racemic substrates, remain underexplored. Conceptually, attractive method for tertiary stereocenter might be abstraction followed donation. However, implementing a strategy poses significant challenges, primarily because products are also reactive if chiral catalyst is unable differentiate between two enantiomers. Herein we report distinct dual photochemical δ- γ-lactams, achieving high enantioenrichment deuterium incorporation despite inherent reactivity products. Mechanistic studies reveal that benzophenone enables nonselective while tetrapeptide-derived thiol dictates enantioselectivity donation step. More importantly, pyridine-based alcohol was found play crucial roles facilitating well enhancing

Language: Английский

---

Dioxazolones as electrophilic amide sources in copper-catalyzed and -mediated transformations

Beilstein Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 21, P. 200 - 216

Published: Jan. 22, 2025

Over the past decade, dioxazolones have been widely used as N -acylamide sources in amidation processes of challenging substrates, typically employing precious transition metals. However, these catalytic systems often present several challenges associated with cost, toxicity, stability, and recyclability. Among 3d metals, copper catalysts gaining increasing attention owing to their abundance, cost-effectiveness, sustainability. Recently, applied chemical transformation dioxazolones, conferring a convenient protocol towards amidated products. This review highlights recent advancements synthetic transformations particular examples salts.

Language: Английский

---

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

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3789 - 3798

Published: Feb. 18, 2025

Language: Английский

---

Recent Advances in Enantioselective Radical Reactions of C(sp³)—H Bond

Chinese Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 45(2), P. 498 - 498

Published: Jan. 1, 2025

Language: Английский

---

Facile, efficient and green phthalimide synthesis in supercritical carbon dioxide

Mendeleev Communications, Journal Year: 2025, Volume and Issue: 35(3), P. 341 - 343

Published: Jan. 1, 2025

Language: Английский

---