Mild and General Conditions for Negishi Cross‐Coupling Enabled by the Use of Palladacycle Precatalysts

Yang, Yang; Oldenhuis, Nathan J.; Buchwald, Stephen L.

doi:10.1002/ange.201207750

Cited by 32 publications

(16 citation statements)

References 57 publications

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“…1 Of these methods, the Pd-catalyzed Suzuki-Miyaura 2 and Negishi 3 cross-coupling have received considerable development over the past 40 years. 1,4 Significant advances in the development of highly active Pd-catalysts 5 to achieve efficient processes have even allowed for these reactions to be employed on industrial scale. 6 In general, bulky electron-rich phosphines 7 and N -heterocyclic carbenes 8,9 have been the ligands of choice to enable these cross-coupling reactions.…”

Section: Introductionmentioning

confidence: 99%

Computationally Assisted Mechanistic Investigation and Development of Pd-Catalyzed Asymmetric Suzuki–Miyaura and Negishi Cross-Coupling Reactions for Tetra-ortho-Substituted Biaryl Synthesis

et al. 2018

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Metal-catalyzed cross-coupling reactions are extensively employed in both academia and industry for the synthesis of biaryl derivatives for applications to both medicine and material science. Application of these methods to prepare tetra-ortho-substituted biaryls leads to chiral atropisomeric products that introduces the opportunity to use catalyst-control to develop asymmetric cross-coupling procedures to access these important compounds. Asymmetric Pd-catalyzed Suzuki-Miyaura and Negishi cross-coupling reactions to form tetra-ortho-substituted biaryls were studied employing a collection of P-chiral dihydrobenzooxaphosphole (BOP) and dihydrobenzoazaphosphole (BAP) ligands. Enantioselectivities of up to 95:5 and 85:15 er were identified for the Suzuki-Miyaura and Negishi cross-coupling reactions, respectively. Unique ligands for the Suzuki-Miyaura reaction vs the Negishi reaction were identified. A computational study on these Suzuki-Miyaura and Negishi cross-coupling reactions enabled an understanding in the differences between the enantiodiscriminating events between these two cross-coupling reactions. These results support that enantioselectivity in the Negishi reaction results from the reductive elimination step, whereas all steps in the Suzuki-Miyaura catalytic cycle contribute to the overall enantioselection with transmetalation and reductive elimination providing the most contribution to the observed selectivities.

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Section: Introductionmentioning

confidence: 99%

Computationally Assisted Mechanistic Investigation and Development of Pd-Catalyzed Asymmetric Suzuki–Miyaura and Negishi Cross-Coupling Reactions for Tetra-ortho-Substituted Biaryl Synthesis

et al. 2018

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“…The analysis is consistent with the literature data. 68 1 H NMR (400 MHz, CDCl 3 ) δ: 8.31 (d, J = 8.00 Hz, 1H), 7.98 (d, J = 7.60 Hz, 1H), 7.93 (d, J = 7.60 Hz, 1H), 7.89 (d, J = 7.60 Hz, 1H), 7.66 (s, 1H), 7.62 (s, 1H), 7.56–7.41 (m, 4H); 13 C{ 1 H} NMR (100 MHz, CDCl 3 ) δ: 140.8, 140.4, 139.4, 137.7, 137.3, 130.8, 125.5, 125.0, 124.9, 124.7, 124.5, 123.7, 123.2, 123.1, 122.3, 121.6.…”

Section: Methodsmentioning

confidence: 99%

Toward Soluble 5,10-Diheterotruxenes: Synthesis and Reactivity of 5,10-Dioxatruxenes, 5,10-Dithiatruxenes, and 5,10-Diazatruxenes

et al. 2020

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The following work presents three general approaches allowing, for the first time, the synthesis of 5,10-diheterotruxene derivatives containing two identical heteroatoms, namely, oxygen OOC , nitrogen NNC , or sulfur SSC . Two of described pathways involve the photocyclization of the corresponding triene 2 as a key step leading to a heptacyclic aromatic system. The third approach is based on the acidic condensation between ninhydrin 14 and benzo[ b ]heteroole 15 . Typical functionalizations of the 5,10-diheterotruxene core have also been presented. In addition, the article discusses the advantages and limitations of the three suggested paths for receiving specific 5,10-diheterotruxene derivatives because the universal method suitable for obtaining molecules with any type of heteroatoms is not known so far.

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“…[15] Both electron-rich and electron-poor arylzinc pivalates (1a,b)aswell as pyridylzinc pivalates [16] (1c-e) gave satisfactory results in reactions using 4mol %Pd(OAc) 2 and 8mol %S Phos, [17] leading to functionalized tyrosines (4a-e)i n5 0-87 %yield (Scheme 2). [15] Both electron-rich and electron-poor arylzinc pivalates (1a,b)aswell as pyridylzinc pivalates [16] (1c-e) gave satisfactory results in reactions using 4mol %Pd(OAc) 2 and 8mol %S Phos, [17] leading to functionalized tyrosines (4a-e)i n5 0-87 %yield (Scheme 2).…”

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confidence: 99%

Late‐Stage Functionalization of Peptides and Cyclopeptides Using Organozinc Reagents

et al. 2019

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We report anew late-stage functionalization of small peptides and cyclopeptides relying on the Negishi crosscoupling of readily prepared iodotyrosine-or iodophenylalanine-containing peptides with aryl-, heteroaryl-, and alkylzinc pivalates or halides.I ns ilico and in vitro determinations of membrane permeability parameters of the modified cyclopeptides showed that in most cases,the solubility was improved by the introduction of polar pyridyl units while the cellmembrane permeability was maintained.Scheme 1. Preparation of modified tyrosine-based peptides 4 starting from tyrosine-containing peptides of type 2.Scheme 2. Negishi cross-coupling of tyrosine derivative 3a with aryland heteroarylzinc pivalates leading to the tyrosines 4a-e. and Albemarle (Frankfurt a. M.) for the generous gift of chemicals. Conflict of interestTheauthors declare no conflict of interest.

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Mild and General Conditions for Negishi Cross‐Coupling Enabled by the Use of Palladacycle Precatalysts

Cited by 32 publications

References 57 publications

Computationally Assisted Mechanistic Investigation and Development of Pd-Catalyzed Asymmetric Suzuki–Miyaura and Negishi Cross-Coupling Reactions for Tetra-ortho-Substituted Biaryl Synthesis

Computationally Assisted Mechanistic Investigation and Development of Pd-Catalyzed Asymmetric Suzuki–Miyaura and Negishi Cross-Coupling Reactions for Tetra-ortho-Substituted Biaryl Synthesis

Toward Soluble 5,10-Diheterotruxenes: Synthesis and Reactivity of 5,10-Dioxatruxenes, 5,10-Dithiatruxenes, and 5,10-Diazatruxenes

Late‐Stage Functionalization of Peptides and Cyclopeptides Using Organozinc Reagents

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