Ambiphilic singlet carbenes: Electron donors and acceptors

Bulletin of the Korean Chemical Society, Journal Year: 2022, Volume and Issue: 43(12), P. 1328 - 1341

Published: Sept. 10, 2022

Abstract The isolation of cyclic(alkyl)(amino)carbenes (CAACs) and N , ′‐diamidocarbenes (DACs) has opened up new avenues in the field carbene chemistry due to their unique properties. CAACs are strong σ‐donors π‐acceptors, whereas DACs extremely π‐acceptors. ambiphilicity carbenes can facilitate applications such as small molecule activation catalysis. Since DACs, several ambiphilic have been synthesized, thereby advancing development chemistry. This review summarizes most relevant findings on until 2022.

Language: Английский

---

EDA mediated S–N bond coupling of nitroarenes and sodium sulfinate salts

Chemical Science, Journal Year: 2022, Volume and Issue: 14(3), P. 525 - 532

Published: Dec. 15, 2022

Despite their long-known photochemical properties and industrial value, the use of nitroarenes as a productive handle in organic synthesis has remained relatively unexplored. More specifically, formation nitrogen-sulfur bonds from remains to be demonstrated. Herein, we report design application sulfinate-nitroarene electron donor-acceptor (EDA) complex its subsequent first light mediated catalyst-free N-hydroxy-sulfonamides. The presence EDA was assessed spectroscopically studied via DFT TD-DFT calculations. A total 32 examples including both withdrawing donating groups were synthesized under our oxygen- water-tolerant conditions.

Language: Английский

---

Heterogeneous V₂O₅/TiO₂-Mediated Photocatalytic Reduction of Nitro Compounds to the Corresponding Amines under Visible Light

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(13), P. 8690 - 8702

Published: June 27, 2023

The hydrogenation of nitro compounds to their corresponding amines is developed using a heterogeneous and recyclable catalyst (V2O5/TiO2) under irradiation blue LED (9 W) at ambient temperature. Hydrazine hydrate used as reductant ethanol solvent, facilitating green, sustainable, low-cost production. synthesis 32 (hetero)arylamines pharmaceutically relevant molecules (five) are described. Significant features the protocol include recyclability, green temperature, gram-scale reactions. Among other aspects studied 1H-NMR-assisted reaction progress monitoring, control experiments for mechanistic studies, applications, recyclability studies. Furthermore, enabled wide functional group tolerance, chemo-selectivity, high yield, low-cost, environmentally benign synthesis.

Language: Английский

---

Sustainable production of active pharmaceutical ingredients from lignin-based benzoic acid derivatives via “demand orientation”

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(10), P. 3791 - 3815

Published: Jan. 1, 2023

Catalytic production of several representative active pharmaceutical ingredients (APIs) from lignin.

Language: Английский

---

Catalytic transfer hydrogenation of substituted nitro-aromatics through in-situ generated Co(0) nanoparticle from Co(II) complexes supported by pentadentate ligands

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 555, P. 113835 - 113835

Published: Feb. 1, 2024

Language: Английский

---

Deoxygenative Cross-Coupling of C(aryl)–O and C(amide)═O Electrophiles Enabled by Chromium Catalysis Using Bipyridine Ligand

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(5), P. 3120 - 3130

Published: Feb. 16, 2023

Deoxygenative cross-coupling between unactivated C–O and unsaturated C═O electrophiles remains an unsolved challenge in synthetic chemistry. Here, we report the deoxygenative of C–O/C═O by reaction aryl esters with amides, enabled chromium catalysis. Inexpensive simple CrCl3 salt combined bipyridine ligand, magnesium reductant, chlorosilane, shows high reactivity promoting coupling bonds involving hydrogen transfer. This provides a strategy to form pharmaceutically interesting diarylmethylated amines, forging C(sp2)–C(sp3) impeding competing ester homocoupling carbonyl reduction that usually occur under reductive conditions. Mechanistic studies based on high-resolution mass spectrometry analysis deuterium-labeling experiments indicate cleavage Cr subsequent silylation leads formation arylated silachromate, which regioselectively adds carbonyls amides through elimination transfer, resulting C(aryl)–O C(amide)═O electrophiles.

Language: Английский

---

Visible-light-induced dual catalysis for divergent reduction of nitro compounds with CO2 radical anion

Chinese Chemical Letters, Journal Year: 2025, Volume and Issue: unknown, P. 110899 - 110899

Published: Jan. 1, 2025

Language: Английский

---

Chemoselective Three‐Component Geminal Cross Couplings of Dihaloalkanes with Cr Catalysis: Rapid Access to Tertiary and Quaternary Alkanes via a Metal–Carbene Intermediate

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(44)

Published: Sept. 14, 2023

Geminal cross couplings using multiple components enable the formation of several different bonds at one site in building tertiary and quaternary alkanes. Nevertheless, there are remaining issues concern-cleavage two geminal control selectivity present challenges. We report here three by reactions dihaloalkanes with organomagnesium chlorosilanes or alkyl tosylates Cr catalysis, affording C-C/C-Si C-C/C-C creation The catalyzed low-cost CrCl2 , enabling sluggishness competitive Kumada-type side homocouplings Grignard reagents, achieving high chemoselectivity. Experimental theoretical studies indicate that C-halide continuously cleaved to afford a metal carbene intermediate, which couples reagent, followed silylation, C-C C-Si via novel inner-sphere radical coupling mechanism. These three-component value-addition synthesis commercial drugs bioactive molecules medicinal chemistry.

Language: Английский

---

Amidophosphine Boranes as Easy Reducing Agents for Efficient Conversion of Nitro Compounds to Primary Amines With Iron Catalyst

Applied Organometallic Chemistry, Journal Year: 2025, Volume and Issue: 39(3)

Published: Feb. 5, 2025

ABSTRACT We report a direct and efficient methodology for the hydroboration of aliphatic aryl nitro compounds using amidophosphine‐borane {(C 6 H 5 )CH 2 N(PPh) (BH 3 ) } in presence iron(II) chloride as catalyst under mild conditions to form primary amines after hydrolysis. Solid amidophosphine‐boranes are user‐friendly readily synthesized, revealing remarkable reducing properties toward comprehensive range compounds. The scalability present approach is defined by performing gram‐scale reactions synthesis different pharmaceuticals like paracetamol benzocaine, demonstrating synthetic applicability current strategy.

Language: Английский

---

Recent Developments in the Reduction of Nitro and Nitroso Compounds

Elsevier eBooks, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Language: Английский

---