scholarly journals Iron-Catalyzed C(sp2)–C(sp3) Cross-Coupling of Aryl Chlorobenzoates with Alkyl Grignard Reagents

Molecules ◽  
2020 ◽  
Vol 25 (1) ◽  
pp. 230 ◽  
Author(s):  
Elwira Bisz ◽  
Michal Szostak
Keyword(s):  
Organic Synthesis ◽  
Nucleophilic Addition ◽  
Functional Group ◽  
High Selectivity ◽  
Cross Coupling ◽  
Environmentally Benign ◽  
Grignard Reagents ◽  
High Importance ◽  
Iron Salts ◽  
The Cross

Aryl benzoates are compounds of high importance in organic synthesis. Herein, we report the iron-catalyzed C(sp2)–C(sp3) Kumada cross-coupling of aryl chlorobenzoates with alkyl Grignard reagents. The method is characterized by the use of environmentally benign and sustainable iron salts for cross-coupling in the catalytic system, employing benign urea ligands in the place of reprotoxic NMP (NMP = N-methyl-2-pyrrolidone). It is notable that high selectivity for the cross-coupling is achieved in the presence of hydrolytically-labile and prone to nucleophilic addition phenolic ester C(acyl)–O bonds. The reaction provides access to alkyl-functionalized aryl benzoates. The examination of various O-coordinating ligands demonstrates the high activity of urea ligands in promoting the cross-coupling versus nucleophilic addition to the ester C(acyl)–O bond. The method showcases the functional group tolerance of iron-catalyzed Kumada cross-couplings.

ChemInform Abstract: Nickel-Butadiene Catalytic System for the Cross-Coupling of Bromoalkanoic Acids with Alkyl Grignard Reagents: A Practical and Versatile Method for Preparing Fatty Acids.

ChemInform ◽  
2013 ◽  
Vol 44 (28) ◽  
pp. no-no
Author(s):  
Takanori Iwasaki ◽  
Kiyokazu Higashikawa ◽  
Vutukuri P. Reddy ◽  
Willbe W. S. Ho ◽  
Yukari Fujimoto ◽  
...  
Keyword(s):  
Fatty Acids ◽  
Catalytic System ◽  
Cross Coupling ◽  
Grignard Reagents ◽  
The Cross

scholarly journals Cross-coupling of dissimilar ketone enolates via enolonium species to afford non-symmetrical 1,4-diketones

2018 ◽  
Vol 14 ◽  
pp. 992-997 ◽  
Author(s):  
Keshaba N Parida ◽  
Gulab K Pathe ◽  
Shimon Maksymenko ◽  
Alex M Szpilman
Keyword(s):  
Organic Synthesis ◽  
Cross Coupling ◽  
Enol Ether ◽  
Enol Ethers ◽  
Ketone Enolates ◽  
The Cross

Due to their closely matched reactivity, the coupling of two dissimilar ketone enolates to form a 1,4-diketone remains a challenge in organic synthesis. We herein report that umpolung of a ketone trimethylsilyl enol ether (1 equiv) to form a discrete enolonium species, followed by addition of as little as 1.2–1.4 equivalents of a second trimethylsilyl enol ether, provides an attractive solution to this problem. A wide array of enolates may be used to form the 1,4-diketone products in 38 to 74% yield. Due to the use of two TMS enol ethers as precursors, an optimization of the cross-coupling should include investigating the order of addition.

Iron catalysed cross-couplings of azetidines – application to the formal synthesis of a pharmacologically active molecule

2015 ◽  
Vol 51 (11) ◽  
pp. 2111-2113 ◽  
Author(s):  
Dixit Parmar ◽  
Lena Henkel ◽  
Josef Dib ◽  
Magnus Rueping
Keyword(s):  
Cross Coupling ◽  
Grignard Reagents ◽  
Active Molecule ◽  
Formal Synthesis ◽  
Iron Catalysis ◽  
The Cross ◽  
Pharmacologically Active

A protocol for the cross-coupling of azetidines with aryl, heteroaryl, vinyl and alkyl Grignard reagents has been developed under iron catalysis. In addition, a short formal synthesis of a pharmacologically active molecule was demonstrated.

scholarly journals Suzuki–Miyaura cross coupling is not an informative reaction to demonstrate the performance of new solvents

2020 ◽  
Vol 16 ◽  
pp. 1001-1005
Author(s):  
James Sherwood
Keyword(s):  
Organic Synthesis ◽  
Propylene Carbonate ◽  
Cross Coupling ◽  
Ethyl Lactate ◽  
Limited Information ◽  
The Cross

The development and study of new solvents has become important due to a proliferation of regulations preventing or limiting the use of many conventional solvents. In this work, the suitability of the Suzuki–Miyaura reaction to demonstrate the usefulness of new solvents was evaluated, including Cyrene™, dimethyl isosorbide, ethyl lactate, 2-methyltetrahydrofuran (2-MeTHF), propylene carbonate, and γ-valerolactone (GVL). It was found that the cross coupling is often unaffected by the choice of solvent, and therefore the Suzuki–Miyaura reaction provides limited information regarding the usefulness of any particular solvent for organic synthesis.

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