ppm level Pd catalytic Suzuki-Miyaura coupling reaction in water and its application in the synthesis of Bixafen DOI
Zhiyong Tan, Tingting Chen, Jiayi Shen

et al.

Tetrahedron, Journal Year: 2025, Volume and Issue: unknown, P. 134464 - 134464

Published: Jan. 1, 2025

Language: Английский

A Sustainable 1-Pot, 3-Step Synthesis of Boscalid Using Part per Million Level Pd Catalysis in Water DOI
Balaram S. Takale,

Ruchita R. Thakore,

Rushil Mallarapu

et al.

Organic Process Research & Development, Journal Year: 2019, Volume and Issue: 24(1), P. 101 - 105

Published: Dec. 3, 2019

Boscalid is an active ingredient in several fungicides marketed by the BASF. Literature approaches use multipot processes, organic solvents, and unsustainable levels of palladium catalysis. Herein disclosed a 1-pot, 3-step route using nanomicelles water as reaction medium very low loading (700 ppm or 0.07 mol %) costly endangered Pd. The sequence developed involves initial Suzuki–Miyaura cross-coupling, product from which not isolated. second step relies on carbonyl iron powder (CIP) reduction aryl nitro group, followed third final involving acylation with required 2-chloronicotinyl chloride. overall isolated yield for these three steps 83%.

Language: Английский

Citations

50
Scalable α-Arylation of Nitriles in Aqueous Micelles using Ultrasmall Pd Nanoparticles: Surprising Formation of Carbanions in Water DOI

Manisha Bihani,

Tharique N. Ansari, Lucie Finck

et al.

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(12), P. 6816 - 6821

Published: April 22, 2020

A scalable synthetic method is described for both the preparation of ultrasmall palladium nanoparticles and their subsequent use in catalyzing an α-arylation reaction nitriles aqueous micelles. This involves intermediacy carbanions or keteniminates, which are presumably stabilized by micellar environment rather than being quenched with water. These Pd thoroughly characterized. Mechanistic studies using 31P NMR spectroscopy revealed binding phosphine ligand surface control experiment confirmed zero-oxidation state palladium. The scope transformation demonstrated over 35 examples, including one at 50 g scale.

Language: Английский

Citations

45
Chemoselective Reductive Aminations in Aqueous Nanoreactors Using Parts per Million Level Pd/C Catalysis DOI

Ruchita R. Thakore,

Balaram S. Takale, Gianluca Casotti

et al.

Organic Letters, Journal Year: 2020, Volume and Issue: 22(16), P. 6324 - 6329

Published: Aug. 3, 2020

Condensation in recyclable water between aldehydes or ketones and amines occurs smoothly within the hydrophobic cores of nanomicelles, resulting imine formation that is subject to subsequent reduction leading, overall, reductive amination. This micellar technology enables synthesis several types pharmaceuticals, a new procedure relies on only 2000 ppm (0.20 mol %) palladium from commercially available Pd/C. A broad range substrates can be used under mild conditions, leading high chemical yields desired secondary tertiary amines.

Language: Английский

Citations

43
N2Phos – an easily made, highly effective ligand designed for ppm level Pd-catalyzed Suzuki–Miyaura cross couplings in water DOI Creative Commons
Nnamdi Akporji,

Ruchita R. Thakore,

Margery Cortes‐Clerget

et al.

Chemical Science, Journal Year: 2020, Volume and Issue: 11(20), P. 5205 - 5212

Published: Jan. 1, 2020

A new, biaryl phosphine-containing ligand, N2Phos, forms a 1 : complex with Pd resulting in an active catalyst at the ppm level for Suzuki–Miyaura couplings water, enabled by aqueous micellar medium. Notably, aryl chlorides are shown to be amenable substrates.

Language: Английский

Citations

40
Environmentally responsible, safe, and chemoselective catalytic hydrogenation of olefins: ppm level Pd catalysis in recyclable water at room temperature DOI
Balaram S. Takale,

Ruchita R. Thakore,

Eugene S. Gao

et al.

Green Chemistry, Journal Year: 2020, Volume and Issue: 22(18), P. 6055 - 6061

Published: Jan. 1, 2020

Textbook catalytic hydrogenations are typically presented as reactions done in organic solvents and oftentimes under varying pressures of hydrogen using specialized equipment.

Language: Английский

Citations

40
Organic synthesis in Aqueous Multiphase Systems — Challenges and opportunities ahead of us DOI
Pascal Hauk, Joanna Wencel‐Delord, Lutz Ackermann

et al.

Current Opinion in Colloid & Interface Science, Journal Year: 2021, Volume and Issue: 56, P. 101506 - 101506

Published: Sept. 21, 2021

Language: Английский

Citations

40
Metal–Micelle Cooperativity: Phosphine Ligand-Free Ultrasmall Palladium(II) Nanoparticles for Oxidative Mizoroki–Heck-type Couplings in Water at Room Temperature DOI Creative Commons
Tharique N. Ansari, Jacek B. Jasiński, David K. Leahy

et al.

JACS Au, Journal Year: 2021, Volume and Issue: 1(3), P. 308 - 315

Published: Jan. 14, 2021

The amphiphile PS-750-M generates stable, phosphine ligand-free, and catalytically active ultrasmall Pd(II) nanoparticles (NPs) from Pd(OAc)2, preventing their precipitation, polymerization, oxidation state changes. directly interacts with NP surfaces, as confirmed by high-resolution mass spectrometry IR spectroscopy, resulting in high stability. Pd cations NPs are most likely held together hydroxides acetate ions. were characterized HRTEM, revealing morphology particle size distribution, HRMS IR, providing evidence for NP–amphiphile interaction. catalytic activity was examined the context of oxidative Mizoroki–Heck-type couplings water at room temperature. Hot filtration, hot extraction, three-phase tests indicate heterogeneous catalysis occurring micellar interface rather than homogeneous solution. NMR studies that stems metal cation−π interactions styrene along transmetalation arylboronic acid, followed insertion β-H elimination to furnish coupled product reoxidation benzoquinone complete cycle. This method is very mild sustainable, both terms synthesis subsequent catalysis, shows broad substrate scope while circumventing need organic solvents this important class couplings.

Language: Английский

Citations

33
Recent progress in copper-free Sonogashira-Hagihara cross-couplings in water DOI Creative Commons
Julia Struwe, Lutz Ackermann, Fabrice Gallou

et al.

Chem Catalysis, Journal Year: 2022, Volume and Issue: 3(1), P. 100485 - 100485

Published: Dec. 22, 2022

Language: Английский

Citations

24
Magnetic nanoparticles-supported palladium catalyzed Suzuki-Miyaura cross coupling DOI
Sandip P. Vibhute,

Pradeep M. Mhaldar,

Rajendra V. Shejwal

et al.

Tetrahedron Letters, Journal Year: 2020, Volume and Issue: 61(11), P. 151594 - 151594

Published: Jan. 8, 2020

Language: Английский

Citations

39
Mild and Robust Stille Reactions in Water using Parts Per Million Levels of a Triphenylphosphine‐Based Palladacycle DOI
Balaram S. Takale,

Ruchita R. Thakore,

Gianluca Casotti

et al.

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(8), P. 4158 - 4163

Published: Nov. 12, 2020

Abstract An inexpensive and new triphenylphosphine‐based palladacycle has been developed as a pre‐catalyst, leading to highly effective Stille cross‐coupling reactions in water under mild reaction conditions. Only 500–1000 ppm of Pd suffices for couplings involving variety aryl/heteroaryl halides with aryl/hetaryl stannanes. Several drug intermediates can be prepared using this catalyst aqueous nanoreactors formed by 2 wt % Brij‐30 water.

Language: Английский

Citations

39