Cross-coupling reactions for environmentally benign synthesis

Efficient C-S and C-N cross-coupling reactions have been developed for regioselective, scalable and environmentally benign synthesis of substituted phenothiazine derivatives. Cross-coupling reactions were demonstrated on various challenging substrates using non-toxic, highly economical, readily available ferric citrate as a catalyst to get desired product with high regioselectivity. Atom economy is the added advantage of this protocol since additional N-protection step before coupling and eventual deprotection of the same to obtain the desired product arenot required. To the best of our knowledge, this is the first report on the use of inexpensive ferric citrate as a catalyst without involving any ligand for the synthesis of regioselectively substituted phenothiazine.

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Nitrosonium-Mediated Phenol–Arene Cross-Coupling Involving Direct C–H Activation

Australian Journal of Chemistry ◽

10.1071/ch16622 ◽

2017 ◽

Vol 70 (4) ◽

pp. 407 ◽

Cited By ~ 4

Author(s):

Anna Eisenhofer ◽

Uta Wille ◽

Burkhard König

Keyword(s):

Cross Coupling ◽

Solvent System ◽

Environmentally Benign ◽

Lithium Nitrate ◽

Coupling Reactions ◽

Substituted Phenols ◽

Cross Coupling Reactions ◽

Inorganic Nitrate ◽

Nitrosonium Ion

The nitrosonium ion (NO+) is a highly versatile nitration and nitrosation reagent, as well as a strong one-electron oxidant. Herein, we describe an environmentally benign and mild method for the in situ formation of NO+ from readily available inorganic nitrate salts, i.e. lithium nitrate, through a finely tuned interplay between formic acid and MeOH, which are used as the solvent system. This methodology was applied to the NO+-induced oxidative C–H activation of methoxy-substituted phenols, which are versatile lignin-derived aromatic feedstocks, to achieve C–C cross-coupling reactions with arenes. The regeneration of NO+ by atmospheric molecular oxygen enables substoichiometric use of the nitrate.

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Manganese-Catalyzed Kumada Cross-Coupling Reactions of Aliphatic Grignard Reagents with N-Heterocyclic Chlorides

Synlett ◽

10.1055/s-0037-1610200 ◽

2018 ◽

Vol 29 (13) ◽

pp. 1700-1706 ◽

Cited By ~ 4

Author(s):

Ellen Matson ◽

Brittney Petel ◽

Merjema Purak

Keyword(s):

Reaction Rate ◽

Metal Salt ◽

Cross Coupling ◽

Environmentally Benign ◽

Coupling Reactions ◽

Reaction Conditions ◽

Heterocyclic Molecules ◽

Cross Coupling Reactions ◽

High Yields ◽

Selective Formation

Herein we report the use of manganese(II) chloride for the catalytic generation of C(sp2)–C(sp3) bonds via Kumada cross-coupling. Rapid and selective formation of 2-alkylated N-heterocyclic complexes were observed in high yields with use of 3 mol% MnCl2THF1.6 and under ambient reaction conditions (21 °C, 15 min to 20 h). Manganese-catalyzed cross-coupling is tolerant toward both electron-donating and electron-withdrawing functional groups in the 5-position of the pyridine ring, with the latter resulting in an increased reaction rate and a decrease in the amount of nucleophile required. The use of this biologically and environmentally benign metal salt as a catalyst for C–C bond formation highlights its potential as a catalyst for the late-stage functionalization of pharmaceutically active N-heterocyclic molecules (e.g., pyridine, pyrazine).

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Nickel–glycerol: an efficient, recyclable catalysis system for Suzuki cross coupling reactions using aryl diazonium salts

New Journal of Chemistry ◽

10.1039/c5nj01833a ◽

2016 ◽

Vol 40 (2) ◽

pp. 1564-1570 ◽

Cited By ~ 11

Author(s):

Jeevan Manohar Bhojane ◽

Sachin Ashok Sarode ◽

Jayashree Milind Nagarkar

Keyword(s):

Bond Formation ◽

Cross Coupling ◽

Environmentally Benign ◽

Diazonium Salts ◽

Coupling Reactions ◽

Formation Reaction ◽

Cross Coupling Reactions

A palladium free, chemoselective and environmentally benign protocol for a C–C bond formation reaction.

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Recent Developments and Perspectives in the C-Se Cross Coupling Reactions

Current Organic Chemistry ◽

10.2174/1385272824999200528130131 ◽

2020 ◽

Vol 24 (11) ◽

pp. 1230-1262 ◽

Cited By ~ 1

Author(s):

Diana Elizabeth Jose ◽

U. S. Kanchana ◽

Thomas V. Mathew ◽

Gopinathan Anilkumar

Keyword(s):

Cross Coupling ◽

Environmentally Benign ◽

Coupling Reactions ◽

Organoselenium Compounds ◽

Bond Forming ◽

Design And Synthesis ◽

Cross Coupling Reactions ◽

Material Interest ◽

Recent Developments ◽

Low Toxicity

: The C-Se bond forming reactions are attractive synthetic strategies for biochemists and synthetic chemists alike for the synthesis of various molecules that are of biological, pharmaceutical and material interest. Therefore, the design and synthesis of organoselenium compounds currently constitute engaging fundamental problems in applied chemistry both in pharmaceutical and academic laboratories. This review discusses the recent works reported in carbon–selenium cross-coupling reactions with the emphasis on the mechanistic aspects of the reactions. The reacting species, the addition of ligands, selection of catalysts, use of suitable solvents, proper setting of reaction time, are well discussed to understand the detailed mechanism. Various simple, economical and environmentally friendly protocols are demonstrated, which ensured product stability, low toxicity, environmentally benign and excellent reactivity for the synthesis of organoselenium compounds. This review covers the scientific literature from 2010 to 2019.

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Rational design of novel ligands for environmentally benign cross-coupling reactions

Pure and Applied Chemistry ◽

10.1351/pac-con-10-08-06 ◽

2011 ◽

Vol 83 (3) ◽

pp. 633-644 ◽

Cited By ~ 14

Author(s):

Oleg M. Demchuk ◽

Katarzyna Kielar ◽

K. Michał Pietrusiewicz

Keyword(s):

Rational Design ◽

Cross Coupling ◽

Phosphine Ligands ◽

Environmentally Benign ◽

Rhodium Complexes ◽

Coupling Reactions ◽

Phosphine Oxides ◽

Mild Conditions ◽

Cross Coupling Reactions ◽

Bismuth Triflate

Transition-metal (TM) complexes of new phosphines, readily prepared by a straight-forward three-step modular synthesis, were successfully employed in difficult cross-coupling reactions conducted under mild conditions (water, “open-flask”, low temperature) that aspire to meet green chemistry criteria. High yielding catalyzed by bismuth or rhodium complexes oxidative arylation of naphthoquinone gave the key 2-arylnaphthoquinone intermediates for facile bismuth triflate-catalyzed Michael addition of secondary phosphine oxides. Subsequent O-methylation and reductions of the resulting products gave access to the target air-stable phosphine ligands in good overall yields (up to 60 %).

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Iron-Catalyzed Cross-Coupling Reactions of Alkyl Grignards with Aryl Chlorobenzenesulfonates

Molecules ◽

10.3390/molecules26195895 ◽

2021 ◽

Vol 26 (19) ◽

pp. 5895

Author(s):

Elwira Bisz

Keyword(s):

Organic Chemistry ◽

Catalytic System ◽

Cross Coupling ◽

Environmentally Benign ◽

Grignard Reagents ◽

Coupling Reactions ◽

Aryl Chlorides ◽

Cross Coupling Reactions ◽

Bioactive Properties ◽

Synthetic Intermediates

Aryl sulfonate esters are versatile synthetic intermediates in organic chemistry as well as attractive architectures due to their bioactive properties. Herein, we report the synthesis of alkyl-substituted benzenesulfonate esters by iron-catalyzed C(sp2)–C(sp3) cross-coupling of Grignard reagents with aryl chlorides. The method operates using an environmentally benign and sustainable iron catalytic system, employing benign urea ligands. A broad range of chlorobenzenesulfonates as well as challenging alkyl organometallics containing β-hydrogens are compatible with these conditions, affording alkylated products in high to excellent yields. The study reveals that aryl sulfonate esters are the most reactive activating groups for iron-catalyzed alkylative C(sp2)–C(sp3) cross-coupling of aryl chlorides with Grignard reagents.

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Ionic Liquids and Ohmic Heating in Combination for Pd-Catalyzed Cross-Coupling Reactions: Sustainable Synthesis of Flavonoids

Molecules ◽

10.3390/molecules25071564 ◽

2020 ◽

Vol 25 (7) ◽

pp. 1564

Author(s):

Vera L. M. Silva ◽

Raquel G. Soengas ◽

Artur M. S. Silva

Keyword(s):

Ionic Liquid ◽

Ohmic Heating ◽

Aqueous Media ◽

Cross Coupling ◽

Chemical Processes ◽

Environmentally Benign ◽

Coupling Reactions ◽

Supported Ionic Liquid ◽

Cross Coupling Reactions ◽

Increasing Demand

In order to meet the increasing demand for environmentally benign chemical processes, we developed a Suzuki–Miyaura reaction protocol based on the combination of ohmic heating (ΩH) and supported ionic liquid phase catalysis (SILPC) in aqueous media. This methodology was applied to the synthesis of a series of flavonoid derivatives, including isoflavones, styrylisoflavones, and diarylalkenylisoflavones.

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