Palladium-catalysed cross-coupling reactions of arylboronic acids with π-deficient heteroaryl chlorides

Ali, Naji M.; McKillop, Alexander; Mitchell, Michael B.; Rebelo, Ricardo Andrade; Wallbank, P. J.

doi:10.1016/s0040-4020(01)80481-6

Cited by 108 publications

(39 citation statements)

References 46 publications

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“…In the inverted HetArB(OH) 2 -ArLG series (entries 11,12), the work on indoles highlights the potential of the DoM-cross-coupling methodology in this underexplored area [28c]. Studies on the ArB(OH) 2 -6-ring HetArLG group (Table 14.6) [48][49][50][51][52][53][54][55] show the not-surprising dominance of pyridines (entries 1-8) some of which, bearing dihalogen substitution patterns, provide cross-coupling selectivity and hence interesting azabiaryls for further manipulation (entries 3, 7). The few entries of heterocycles such as quinolines (entries 4), pyrimidines (entries 9, 10), and pyrones (entry 11) are perhaps harbingers of generalizations.…”

Section: → Boron Transmetallation the Suzuki-miyaura Cross-couplimentioning

confidence: 99%

The Directed Ortho Metallation (DoM)–Cross‐Coupling Nexus. Synthetic Methodology for the Formation of Aryl–Aryl and Aryl–Heteroatom–Aryl Bonds

Snieckus¹,

Anctil²

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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Section: → Boron Transmetallation the Suzuki-miyaura Cross-couplimentioning

confidence: 99%

The Directed Ortho Metallation (DoM)–Cross‐Coupling Nexus. Synthetic Methodology for the Formation of Aryl–Aryl and Aryl–Heteroatom–Aryl Bonds

Snieckus¹,

Anctil²

2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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“…We have recently described (12) the synthesis of 2,4,7-trisubstituted quinoline 5-lipoxygenase inhibitors using, as one of the key steps, the regioselective Suzuki cross-coupling reaction of 4,7-dichloroquinoline (1a) with arylboronic acids. As originally described by Mitchell and co-workers (6), the reaction of 1a with 1.1 equiv. of phenylboronic acid (2) catalyzed by Pd(Ph 3 P) 4 (3%) in refluxing aqueous ethanol -benzene and in the presence of Na 2 CO 3 provided, after 48 h, 7-chloro-4-phenylquinoline (3) in 82% isolated yield (Scheme 1).…”

Section: Introductionmentioning

confidence: 96%

“…The use of heteroaryl chlorides as one of the coupling partners has seen increasing utility (6)(7)(8)(9)(10)(11) and is attractive since the starting materials are often more readily available than the corresponding bromides or iodides. We have recently described (12) the synthesis of 2,4,7-trisubstituted quinoline 5-lipoxygenase inhibitors using, as one of the key steps, the regioselective Suzuki cross-coupling reaction of 4,7-dichloroquinoline (1a) with arylboronic acids.…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, the observation of 4 in the reaction of 1a and 2 was not completely unexpected. Since we required an efficient cross-coupling procedure that would bring about regioselective monofunctionalization of a quinoline (6,7,(13)(14)(15)(16)(17), such as 1a, without consuming more elaborate boronic acids by the production of bis-addition products, we undertook a more detailed study of the reactions of 1a and the corresponding iodide 1b to optimize the formation of 3. The results of this study are presented here.…”

Section: Introductionmentioning

confidence: 99%

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Comparison of the Suzuki cross-coupling reactions of 4,7-dichloroquinoline and 7-chloro-4-iodoquinoline with arylboronic acids using phosphine-free palladium catalysis in water

Friesen¹,

Trimble²

2004

Can. J. Chem.

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4,7-Dichloroquinoline (1a) and 7-chloro-4-iodoquinoline (1b) undergo Suzuki cross-coupling reactions with arylboronic acids catalyzed by phosphine-free palladium acetate in boiling water. Using phenylboronic acid (2), the reaction of 1a provides 7-chloro-4-phenylquinoline (3) (78%) together with diphenylquinoline (4) (12%), while 1b reacts in a much more regioselective fashion and provides 3 in 98% isolated yield. Although 1b undergoes a more regioselective Suzuki reaction than 1a, additional important observations are that the overall reaction of 1b with 2 is three times slower than 1a and that the reaction occurs in the absence of tetrabutylammonium bromide. Using optimized reaction conditions, a variety of aryl and vinylboronic acids undergo regioselective Suzuki cross-coupling with 1b to provide the products 7, 10, and 11 in good to excellent yield.Résumé : La 4,7-dichloroquinoléine (1a) et la 7-chloro-4-iodoquinoléine (1b) subissent des réactions de couplage de Suzuki avec les acides arylboroniques qui sont catalysées par de l'acétate de palladium sans phosphine dans de l'eau bouillante. Avec l'acide phénylboronique (2), la réaction du composé 1a fournit la 7-chloro-4-phénylquinoléine (3) (78%) aux côtés de diphénylquinoléine (4) (12%) alors que le composé 1b réagit d'une façon beaucoup plus régiosé-lective et fournit le composé 3 avec un rendement de 98% en produit isolé. Même si le composé 1b donne lieu à une réaction de Suzuki plus régiosélective que celle du composé 1a, des observations importantes additionnelles sont que la vitesse globale du composé 1b avec 2 est trois fois plus lente que celle du composé 1a et que la réaction se produit en l'absence de bromure de tétrabutylammonium. Utilisant des conditions réactionnelles optimisées, une variété d'acides aryl-et vinylboroniques donnent lieu à des réactions régiosélectives de couplage croisé de Suzuki avec le composé 1b et elles fournissent les produits 7, 10 et 11 avec des rendements allant de bons à excellents.

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“…73) Next, we investigated the cross coupling reaction using a palladium-complex, which is often a superior catalyst for certain aryl chlorides. [74][75][76] The coupling reaction resulted in a slightly reduced yield in the presence of 3 mol% PdCl 2 (cod) ( Table 1, entry 6). When the mixture was heated to 80°C for 10 h using 3 mol% Pd(PPh 3 ) 4 under basic conditions, however, the target compound 8, accompanied by less than 1% of the homo-coupling product, was obtained in 96% yield.…”

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confidence: 99%

Application of the Lewis Acid-Lewis Base Bifunctional Asymmetric Catalysts to Pharmaceutical Syntheses: Stereoselective Chiral Building Block Syntheses of Human Immunodeficiency Virus (HIV) Protease Inhibitor and .BETA.3-Adenergic Receptor Agonist

Nogami

Kanai

Shibasaki

2003

CHEMICAL & PHARMACEUTICAL BULLETIN

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Chiral building block syntheses of promising drugs were achieved using two types of catalytic stereoselective cyanosilylations of aldehydes promoted by Lewis acid-Lewis base bifunctional catalysts 1 and 2 as the key steps (diastereoselective cyanosilylation of amino aldehyde and enantioselective cyanosilylation). In the first part of this article, syntheses of chiral building blocks (6) of Atazanavir (3: human immunodeficiency virus (HIV) protease inhibitor) using the bifunctional catalyst 2 are discussed. The reaction of Boc-protected phenylalaninal 21 in the presence of 1 mol% catalyst 2 selectively afforded the anti isomer 22 as the major product (diastereomeric ratio=97 : 3), which was successively converted to the corresponding epoxide 6 in six steps. In the second part, we describe a chiral building block synthesis of beta(3)-adrenergic receptor agonists. The enantioselective cyanosilylation of 3-chlorobenzaldehyde (38) with 9 mol% catalyst 1 gave the chiral cyanohydrin 39, which was converted to beta-hydroxyethylamine 40 by reduction. Moreover, the chiral ligand of catalyst 1 could be recovered without column chromatography and reused without decreasing its activity.

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Palladium-catalysed cross-coupling reactions of arylboronic acids with π-deficient heteroaryl chlorides

Cited by 108 publications

References 46 publications

The Directed Ortho Metallation (DoM)–Cross‐Coupling Nexus. Synthetic Methodology for the Formation of Aryl–Aryl and Aryl–Heteroatom–Aryl Bonds

The Directed Ortho Metallation (DoM)–Cross‐Coupling Nexus. Synthetic Methodology for the Formation of Aryl–Aryl and Aryl–Heteroatom–Aryl Bonds

Comparison of the Suzuki cross-coupling reactions of 4,7-dichloroquinoline and 7-chloro-4-iodoquinoline with arylboronic acids using phosphine-free palladium catalysis in water

Application of the Lewis Acid-Lewis Base Bifunctional Asymmetric Catalysts to Pharmaceutical Syntheses: Stereoselective Chiral Building Block Syntheses of Human Immunodeficiency Virus (HIV) Protease Inhibitor and .BETA.3-Adenergic Receptor Agonist

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