Surfactant-Dependent Partitioning of Organics in Aqueous–Organic Reaction Systems DOI Creative Commons
Y. F. Zhang, Suzanne A. Blum

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(11), P. 8267 - 8271

Published: May 16, 2024

A fluorescence lifetime imaging microscopy (FLIM) technique characterizes surfactant-dependent partitioning of organics in a system that mimics Negishi-like cross-coupling reaction water, under synthetic concentrations, with emulsion droplets. Experimental data were not predictable from simple hydrophilic–lipophilic balances. The ionic surfactant cetrimonium chloride suppressed the reactivity metallic zinc surface, presumably through competitive binding and concurrent coating, finding may contribute to reduced performance surfactants bench-scale coupling reaction.

Language: Английский

Aqueous Micelles as Solvent, Ligand, and Reaction Promoter in Catalysis DOI Creative Commons

Jagdeep K. Virdi,

Ashish Dusunge,

Sachin Handa

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(2), P. 301 - 317

Published: Jan. 16, 2024

Water is considered to be the most sustainable and safest solvent. Micellar catalysis a significant contributor chemistry in water. It promotes pathways involving water-sensitive intermediates transient catalytic species under micelles' shielding effect while also replacing costly ligands dipolar-aprotic solvents. However, there lack of critical information about micellar catalysis. This includes why it works better than traditional organic solvents, specific rules differ from those conventional catalysis, how limitations can addressed future. Perspective aims highlight current gaps our understanding provide an analysis designer surfactants' origin essential components. will fundamental including aqueous micelles simultaneously perform multiple functions such as solvent, ligand, reaction promoter.

Language: Английский

Citations

29

Precision Synthesis of Polysarcosine via Controlled Ring-Opening Polymerization of N-Carboxyanhydride: Fast Kinetics, Ultrahigh Molecular Weight, and Mechanistic Insights DOI
Shuo Wang, Mingyuan Lu,

Sikang Wan

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(8), P. 5678 - 5692

Published: Feb. 15, 2024

The rapid and controlled synthesis of high-molecular-weight (HMW) polysarcosine (pSar), a potential polyethylene glycol (PEG) alternative, via the ring-opening polymerization (ROP) N-carboxyanhydride (NCA) is rare challenging. Here, we report well-controlled ROP sarcosine NCA (Sar-NCA) that catalyzed by various carboxylic acids, which accelerate rate up to 50 times, enables robust pSar with an unprecedented ultrahigh molecular weight (UHMW) 586 kDa (DP ∼ 8200) exceptionally narrow dispersity (D̵) below 1.05. Mechanistic experiments density functional theory calculations together elucidate role acid as bifunctional catalyst significantly facilitates proton transfer processes avoids charge separation suggest ring opening NCA, rather than decarboxylation, rate-determining step. UHMW demonstrates improved thermal mechanical properties over low-molecular-weight counterparts. This work provides simple yet highly efficient approach generates new fundamental understanding useful not only for Sar-NCA but also other NCAs.

Language: Английский

Citations

21

Towards a sustainable tomorrow: advancing green practices in organic chemistry DOI
Sudripet Sharma, Fabrice Gallou, Sachin Handa

et al.

Green Chemistry, Journal Year: 2024, Volume and Issue: 26(11), P. 6289 - 6317

Published: Jan. 1, 2024

Chemistry in water, leveraging its solvent properties, provides a safer and more sustainable alternative to traditional organic methods.

Language: Английский

Citations

18

The green chemistry paradigm in modern organic synthesis DOI
Sergei G. Zlotin, Ksenia S. Egorova, Valentine P. Ananikov

et al.

Russian Chemical Reviews, Journal Year: 2023, Volume and Issue: 92(12), P. RCR5104 - RCR5104

Published: Dec. 1, 2023

After the appearance of green chemistry concept, which was introduced in vocabulary early 1990s, its main statements have been continuously developed and modified. Currently, there are 10–12 cornerstones that should form basis for an ideal chemical process. This review analyzes accumulated experience achievements towards design products processes reduce or eliminate use generation hazardous substances. The presents views leading Russian scientists specializing various fields this subject, including homogeneous heterogeneous catalysis, fine basic organic synthesis, electrochemistry, polymer chemistry, based on bio-renewable feedstocks energetic compounds materials. A new approach to quantitative evaluation environmental friendliness by authors is described. <br> bibliography includes 1761.

Language: Английский

Citations

39

Is Micellar Catalysis Green Chemistry? DOI Creative Commons
Fabrizio Fabris, Markus Illner, Jens‐Uwe Repke

et al.

Molecules, Journal Year: 2023, Volume and Issue: 28(12), P. 4809 - 4809

Published: June 16, 2023

Many years ago, twelve principles were defined for carrying out chemical reactions and processes from a green chemistry perspective. It is everyone’s endeavor to take these points into account as far possible when developing new or improving existing ones. Especially in the field of organic synthesis, area research has thus been established: micellar catalysis. This review article addresses question whether catalysis by applying reaction media. The shows that many can be transferred an solvent medium, but surfactant also crucial role solubilizer. Thus, carried much more environmentally friendly manner with less risk. Moreover, surfactants are being reformulated their design, degradation add extra advantages match all chemistry.

Language: Английский

Citations

23

Recent Highlights in Micellar Catalysis: An Industrial Outlook DOI
Tharique N. Ansari, Guolin Xu, Andrew Z. Preston

et al.

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(4), P. 816 - 830

Published: March 14, 2024

From the context of sustainability, contemporary synthetic organic chemistry practices require significant transformation, as indicated by various sustainability matrices like atom economy, process mass intensity (PMI), E-factor, and DOZN. These factors have evidently unveiled inherent inefficiencies intrinsic to conventional protocols identified solvents principal causative agent. In response, utilization water a primary reaction medium for transformations has emerged an appealing alternative. This approach flourished with emergence micellar catalysis, where amphiphilic molecules alter bulk aqueous medium's solvation properties promote desired chemical transformation under milder sustainable conditions. After 2010, this technology gained considerable momentum established foundational framework performing reactions conditions, consequently mitigating dependency on hazardous solvents. perspective, recent advances in field catalysis will be discussed industrial applications, along future directions challenges associated regime.

Language: Английский

Citations

9

Ligated Pd-Catalyzed Aminations of Aryl/Heteroaryl Halides with Aliphatic Amines under Sustainable Aqueous Micellar Conditions DOI Creative Commons
Karthik S. Iyer,

Rahul D. Kavthe,

R.M. Lammert

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(2), P. 680 - 689

Published: Feb. 12, 2024

Sustainable technology for constructing Pd-catalyzed C–N bonds involving aliphatic amines is reported. A catalytic system that relies on low levels of recyclable precious metal, a known and commercially available ligand, aqueous medium are combined, leading to newly developed procedure. This new can be used in ocean water with equal effectiveness. Applications highly challenging reaction partners constituting late-stage functionalization documented, as short but efficient synthesis the drug naftopidil. Comparisons existing aminations highlight many advances being offered.

Language: Английский

Citations

8

On the role of surfactants: rethinking “aqueous” chemistry DOI
Bruce H. Lipshutz

Green Chemistry, Journal Year: 2023, Volume and Issue: 26(2), P. 739 - 752

Published: Dec. 11, 2023

Some of the latest technological developments involving chemistry in water are discussed.

Language: Английский

Citations

21

Nanoparticles as Heterogeneous Catalysts for ppm Pd-Catalyzed Aminations in Water DOI Creative Commons
Karthik S. Iyer,

Rahul D. Kavthe,

Yuting Hu

et al.

ACS Sustainable Chemistry & Engineering, Journal Year: 2024, Volume and Issue: 12(5), P. 1997 - 2008

Published: Jan. 22, 2024

A general protocol employing heterogeneous catalysis has been developed that enables ppm of Pd-catalyzed C-N cross-coupling reactions under aqueous micellar catalysis. new nanoparticle catalyst containing specifically ligated Pd, in combination with nanoreactors composed the designer surfactant Savie, a biodegradable amphiphile, catalyzes bond formations recyclable water. variety coupling partners, ranging from highly functionalized pharmaceutically relevant APIs to educts Merck Informer Library, readily participate these environmentally responsible, sustainable reaction conditions. Other key features associated this report include low levels residual Pd found products, recyclability medium, use ocean water as an alternative source options for pseudohalides and

Language: Английский

Citations

7

Chemistry in Water Reproducibility Study: Learnings from a Precompetitive, Multicompany Collaboration DOI
Richard J. Fox, J. Daniel Bailey, Jennifer V. Obligacion

et al.

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(4), P. 978 - 1002

Published: March 15, 2024

Despite the reported successes and advantages involving use of amphiphilic surfactants, most notably TPGS-750-M, to enable a multitude synthetic transformations be conducted in water, implementation this methodology within pharmaceutical industry has been relatively limited. In paper, we will disclose key results learnings from multicompany collaboration focused on reproducibility study some commonly used reaction types industry, specifically amidation, SNAr, nitro reduction, reductive amination, multiple Pd-catalyzed water. The presentation not just originally TPGS-750-M conditions but also under water-only control with three different as well both small (i.e., ≤500 mg) mid (∼10 g) scales.

Language: Английский

Citations

7