Cu-Mediated Ullmann-Type Cross-Coupling and Industrial Applications in Route Design, Process Development, and Scale-up of Pharmaceutical and Agrochemical Processes

Organic Process Research & Development, Год журнала: 2022, Номер 26(6), С. 1690 - 1750

Опубликована: Май 24, 2022

Cu-mediated Ullmann-type cross-coupling has experienced significant advances over the last century since seminal publication by Ullmann in 1901. These have significantly expanded scope of original classical coupling aryl halides for formation diaryl compounds to include carbon–heteroatom and other carbon–carbon bonds. The introduction bidentate ligands drastically improved performance this class transformations enable milder reaction conditions that can tolerate a wide range sensitive functional groups. Recent development more powerful second-generation further allowed less reactive chlorides proceed smoothly realized low catalyst ligand loadings broad reactions. As result these breakthrough past decades, reactions been frequently implemented academic research found ubiquitous industrial applications including preparation pharmaceutical agrochemical products. This review provides an overview selected general (C–N, C–O, C–S, C–P) bonds their route design, process development, scale-up processes.

Язык: Английский

---

Nickel‐Catalyzed Sulfonylation of Aryl Bromides Enabled by Potassium Metabisulfite as a Uniquely Effective SO₂ Surrogate

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(19)

Опубликована: Март 10, 2023

The development and mechanistic investigation of a nickel-catalyzed sulfonylation aryl bromides is disclosed. reaction proceeds in good yields for variety substrates utilizes an inexpensive, stench-free, inorganic sulfur salt (K2 S2 O5 ) as uniquely effective SO2 surrogate. active oxidative addition complex was synthesized, isolated, fully characterized by combination NMR spectroscopy X-ray crystallography analysis. use the isolated both stoichiometric catalytic reactions revealed that insertion occurs via dissolved , likely released upon thermal decomposition K2 . Key to success role reservoir slowly released, thus preventing catalyst poisoning.

Язык: Английский

---

Diversification of Pharmaceutical Manufacturing Processes: Taking the Plunge into the Non-PGM Catalyst Pool

ACS Catalysis, Год журнала: 2024, Номер 14(13), С. 9708 - 9733

Опубликована: Июнь 13, 2024

Recent global events have led to the cost of platinum group metals (PGMs) reaching unprecedented heights. Many chemical companies are therefore starting seriously consider and evaluate if where they can substitute PGMs for non-PGMs in their catalytic processes. This review covers recent highly relevant applications non-PGM catalysts modern pharmaceutical industry. By highlighting these selected successful examples non-PGM-catalyzed processes from literature, we hope emphasize enormous potential catalysis inspire further development within this field enable technology progress toward manufacturing We also present some historical contexts perceived advantages challenges implementing environment.

Язык: Английский

---

Recent Advances in Non-Precious Metal Catalysis

Organic Process Research & Development, Год журнала: 2022, Номер 26(8), С. 2281 - 2310

Опубликована: Авг. 2, 2022

This review provides a summary of recently published developments in the field nonprecious metal catalysis (NPMC) and highlights range synthetic applications captured research between July October 2021. is an installment series on this area briefing Ni, Cu, Fe, Co catalysis. There has been evident increase publications NPMC, which indicates widespread interest among laboratories academia industry development utilization catalytic these metals.

Язык: Английский

---

Recent Advances in Nonprecious Metal Catalysis

Organic Process Research & Development, Год журнала: 2020, Номер 24(6), С. 909 - 915

Опубликована: Май 14, 2020

Nonprecious metal catalysis is a highly active area of research for both industrial and academic laboratories. New methods that efficiently generate useful functionality in cost-effective, high yielding, environmentally friendly ways naturally garner attention from process chemists many different industries. This series highlights summarizes literature on the general topic nonprecious over four-month timeframes will focus major trends field are interest pharmaceutical industry. The first installment selected transformations using copper, nickel, iron catalysts.

Язык: Английский

---

Recent Advances in Nonprecious Metal Catalysis

Organic Process Research & Development, Год журнала: 2021, Номер 25(7), С. 1471 - 1495

Опубликована: Июнь 18, 2021

This review summarizes recent developments and synthetic applications of nonprecious metal catalysis (NPMC) published between July October 2020. It is the next installment series on this topic briefing advancements in utility Ni, Cu, Fe catalysis. The continued increase number publications area attests to wide interest among academic industrial research laboratories advancing catalytic these earth-abundant metals.

Язык: Английский

---

Enantioselective Cross‐couplings between Halide Derivatives and Organometallics by Using Iron and Cobalt Catalysts: Formation of C−C Bonds

Chemistry - A European Journal, Год журнала: 2021, Номер 27(43), С. 11021 - 11029

Опубликована: Май 20, 2021

Abstract This review highlights the recent achievements of iron‐ and cobalt‐catalyzed enantioselective cross‐couplings halide derivatives with organometallic reagents for construction C‐C bonds. Synthetic applications to natural products biologically active compounds are also covered showing power these in organic synthesis.

Язык: Английский

---

Si–Cl σ-Bond Cleavage by an Fe(0) Complex with Two Steps of One-Electron Transfer toward Hydrosilane Formation from Tetrachlorosilane

JACS Au, Год журнала: 2025, Номер 5(4), С. 2033 - 2039

Опубликована: Март 17, 2025

Iron catalysts exhibit unique reactivity that has not been found in precious metal catalysts. Herein, a new strategy for strong Si-Cl σ-bond cleavage of tetrachlorosilane (SiCl4) was successful using [{Fe(PNNP)}2(μ-N2)] (PNNP = 2,9-bis((diphenylphosphino)methyl)-1,10-phenanthroline). The resulting oxidative addition product [Fe(SiCl3)(Cl)(PNNP)] fully identified, establishing the first example an air-sensitive iron(0) complex. Theoretical study revealed occurs with radical character through two steps single-electron transfer from [Fe(PNNP)] to σ* antibonding orbital, which differs usual concerted addition. This reaction successfully applied HSiCl3 formation SiCl4 and 1,10-dihydroanthracene via hydrogen atom (HAT). Thus, we succeeded performing Fe(0) complex its application hydrosilane synthesis mild source. is expected be active as catalyst other difficult reaction.

Язык: Английский

---

Homoleptic Cobalt(II) Phenoxyimine Complexes for Hydrosilylation of Aldehydes and Ketones without Base Activation of Cobalt(II)

Organometallics, Год журнала: 2021, Номер 40(9), С. 1379 - 1387

Опубликована: Апрель 28, 2021

Air-stable, easy to prepare, homoleptic cobalt(II) complexes bearing pendant-modified phenoxyimine ligands were synthesized and determined. The exhibited high catalytic performance for reducing aldehydes ketones via hydrosilylation, where a hydrosilane amount of the complex added under base-free conditions. reaction proceeded even in presence excess water, excellent functional-group tolerance was observed. Subsequent hydrolysis gave alcohol yields. Moreover, H2O had critical role activation Co(II) catalyst with hydrosilane. Several additional results also indicated that center acts as an active hydrosilylation ketones.

Язык: Английский

---

Recent Advances in Nonprecious Metal Catalysis

Organic Process Research & Development, Год журнала: 2021, Номер 25(8), С. 1802 - 1815

Опубликована: Авг. 10, 2021

Язык: Английский

---