ChemInform Abstract: Lewis Acid Assisted Nickel-Catalyzed Cross-Coupling of Aryl Methyl Ethers by C-O Bond-Cleaving Alkylation: Prevention of Undesired β-Hydride Elimination.

AbstractA convergent synthesis of IMMH002 in 36% overall yield starting from bromobenzene is described with a key Suzuki–Miyaura cross-coupling reaction used to provide a crucial intermediate. The route does not require column chromatography and solves the most intractable quality problem caused by a homologue by-product in the original linear synthesis. Furthermore, reducing the use of Lewis acid mediated reactions improves the environmental impact of the synthesis and reduces overall waste. The new route described herein is more efficient, convenient, reliable, and economically more viable when compared to the previously reported linear route.

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Cross‐Coupling Reaction of Alkenyl Sulfoximines and Alkenyl Aminosulfoxonium Salts with Organozincs by Dual Nickel Catalysis and Lewis Acid Promotion

Chemistry - A European Journal ◽

10.1002/chem.201901163 ◽

2019 ◽

Vol 25 (35) ◽

pp. 8371-8386 ◽

Cited By ~ 1

Author(s):

Irene Erdelmeier ◽

Gerd Bülow ◽

Chang‐Wan Woo ◽

Jürgen Decker ◽

Gerhard Raabe ◽

...

Keyword(s):

Lewis Acid ◽

Coupling Reaction ◽

Cross Coupling ◽

Nickel Catalysis ◽

Cross Coupling Reaction

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Lewis Acid-Promoted Suzuki Reaction using Palladium Chloride Anchored on a Polymer as a Catalyst

Australian Journal of Chemistry ◽

10.1071/ch08066 ◽

2008 ◽

Vol 61 (8) ◽

pp. 610 ◽

Cited By ~ 12

Author(s):

Guozhi Fan ◽

Hanjun Zhang ◽

Siqing Cheng ◽

Zhandong Ren ◽

Zhijun Hu ◽

...

Keyword(s):

Catalytic Activity ◽

Lewis Acid ◽

Lewis Acids ◽

Heterogeneous Catalysts ◽

Suzuki Reaction ◽

Cross Coupling ◽

Palladium Chloride ◽

Coupling Reactions ◽

Cross Coupling Reactions ◽

Recoverable Catalyst

Palladium chloride anchored on polystyrene modified by 5-amino-1,10-phenanthroline was prepared and used as an efficient recoverable catalyst for Suzuki cross-coupling reactions. The heterogeneous catalysts can be easily separated from the reaction mixture and reused for five cycles without significant Pd leaching and loss of catalytic activity. Rate enhancement in the Suzuki reaction by Lewis acids was also studied.

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Nickel-Catalyzed Cross-Coupling of Aryl Methyl Ethers with Aryl Boronic Esters

Angewandte Chemie ◽

10.1002/ange.200801447 ◽

2008 ◽

Vol 120 (26) ◽

pp. 4944-4947 ◽

Cited By ~ 104

Author(s):

Mamoru Tobisu ◽

Toshiaki Shimasaki ◽

Naoto Chatani

Keyword(s):

Cross Coupling ◽

Boronic Esters ◽

Aryl Methyl

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Ether Synthesis through Reductive Cross-Coupling of Ketones with Alcohols Using Me2SiHCl as both Reductant and Lewis Acid

Synlett ◽

10.1055/s-0036-1590838 ◽

2017 ◽

Vol 28 (18) ◽

pp. 2425-2428 ◽

Cited By ~ 1

Author(s):

Bill Morandi ◽

Yong Lee

Keyword(s):

Functional Groups ◽

Lewis Acid ◽

Carbonyl Compounds ◽

Cross Coupling ◽

Wide Range ◽

Direct Cross ◽

Sterically Hindered ◽

Polar Functional Groups ◽

Ether Synthesis ◽

Dialkyl Ethers

We report that a Lewis acidic silane, Me2SiHCl, can mediate the direct cross-coupling of a wide range of carbonyl compounds with alcohols to form dialkyl ethers. The reaction is operationally simple, tolerates a range of polar functional groups, can be utilized to make sterically hindered ethers, and is extendable to sulfur and nitrogen nucleophiles.

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Ni(COD)(DMFU): A Heteroleptic 16-Electron Precatalyst for 1,2-Diarylation of Alkenes

Synlett ◽

10.1055/a-1344-6040 ◽

2021 ◽

Author(s):

Nana Kim ◽

Van T. Tran ◽

Omar Apolinar ◽

Steven Wisniewski ◽

Martin Eastgate ◽

...

Keyword(s):

Nickel Complex ◽

Active Catalyst ◽

Cross Coupling ◽

Reductive Elimination ◽

Coupling Reactions ◽

Beneficial Effects ◽

Cross Coupling Reactions ◽

Growing Body ◽

Hydride Elimination

Electron-deficient olefin (EDO) ligands are known to promote a variety of nickel-catalyzed cross-coupling reactions, presumably by accelerating the reductive elimination step and preventing undesired β-hydride elimination. While there is a growing body of experimental and computational evidence elucidating the beneficial effects of EDO ligands, significant gaps remain in our understanding of the underlying coordination chemistry of the Ni–EDO species involved. In particular, most procedures rely on in situ assembly of the active catalyst, and there is a paucity of pre-ligated Ni-EDO precatalysts. Herein, we investigate the 16-electron, heteroleptic nickel complex, Ni(COD)(DMFU), and examine the performance of this complex as a precatalyst in 1,2-diarylation of alkenes.

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Palladium-catalyzed cross coupling reactions of 4-bromo-6H-1,2-oxazines

Beilstein Journal of Organic Chemistry ◽

10.3762/bjoc.5.44 ◽

2009 ◽

Vol 5 ◽

Cited By ~ 5

Author(s):

Reinhold Zimmer ◽

Elmar Schmidt ◽

Michal Andrä ◽

Marcel-Antoine Duhs ◽

Igor Linder ◽

...

Keyword(s):

Lewis Acid ◽

Cross Coupling ◽

Pyridine Derivative ◽

Coupling Reactions ◽

Cross Coupling Reactions ◽

Palladium Catalyzed

A number of 4-aryl- and 4-alkynyl-substituted 6H-1,2-oxazines 8 and 9 have been prepared in good yields via cross coupling reactions of halogenated precursors 2, which in turn are easily accessible by bromination of 6H-1,2-oxazines 1. Lewis-acid promoted reaction of 1,2-oxazine 9c with 1-hexyne provided alkynyl-substituted pyridine derivative 12 thus demonstrating the potential of this approach for the synthesis of pyridines.

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Synthesis of 2-Alkenyl-Tethered Anilines

Synthesis ◽

10.1055/s-0036-1589002 ◽

2017 ◽

Vol 49 (13) ◽

pp. 2873-2888 ◽

Cited By ~ 3

Author(s):

Scott Denmark ◽

Hyung Chi

Keyword(s):

Lewis Acid ◽

Cross Coupling ◽

Aryl Halides ◽

Cope Rearrangement ◽

The Third ◽

Cross Metathesis ◽

Direct Cross ◽

Palladium Catalyzed

Three general routes for the synthesis of (E)-2-alkenyl-tethered anilines have been developed. The first route involves a 3-aza-Cope rearrangement of N-allylic anilines in the presence of a Lewis acid. The requisite N-allylic anilines were prepared by the addition of vinylmagnesium reagents to the corresponding aldimines. The second route details a direct cross-metathesis of 2-allylic or 2-homoallylic anilines with styrenes. The third route involves a palladium-catalyzed C–N cross-coupling of aryl halides. Taken together, these three strategies allowed access to the requisite aniline substrates with pendant alkenes at the 2-position with excellent trans selectivities.

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