Palladium‐Catalyzed Asymmetric Allylic Alkylations with Toluene Derivatives as Pronucleophiles

Mao, Jianyou; Zhang, Jiadi; Jiang, Hui; Bellomo, Ana; Zhang, Mengnan; Gao, Zidong; Dreher, Spencer D.; Walsh, Patrick J.

doi:10.1002/anie.201509917

Cited by 68 publications

(25 citation statements)

References 48 publications

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“…By analogy to the allylation of 2-methylpyridines, the group of Walsh used toluene derivatives as pro-nucleophiles, which were activated by complexation with chromium tricarbonyl ( Scheme 144 ). 436 …”

Section: Asymmetric Allylic Substitutionmentioning

confidence: 99%

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Pàmies

Margalef

Cañellas³

et al. 2021

Chem. Rev.

360

202

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This Review compiles the evolution, mechanistic understanding, and more recent advances in enantioselective Pd-catalyzed allylic substitution and decarboxylative and oxidative allylic substitutions. For each reaction, the catalytic data, as well as examples of their application to the synthesis of more complex molecules, are collected. Sections in which we discuss key mechanistic aspects for high selectivity and a comparison with other metals (with advantages and disadvantages) are also included. For Pd-catalyzed asymmetric allylic substitution, the catalytic data are grouped according to the type of nucleophile employed. Because of the prominent position of the use of stabilized carbon nucleophiles and heteronucleophiles, many chiral ligands have been developed. To better compare the results, they are presented grouped by ligand types. Pd-catalyzed asymmetric decarboxylative reactions are mainly promoted by PHOX or Trost ligands, which justifies organizing this section in chronological order. For asymmetric oxidative allylic substitution the results are grouped according to the type of nucleophile used.

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Section: Asymmetric Allylic Substitutionmentioning

confidence: 99%

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Pàmies

Margalef

Cañellas³

et al. 2021

Chem. Rev.

360

202

View full text Add to dashboard Cite

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“…26 This strategy was also successful in allylic substitution reactions with toluene derivatives activated with Cr(CO 3 ). 27,28 While these reactions were successful, they required generation of a stoichiometric, stable metal arene adduct. The ultimate goal, however, is to develop a dual catalytic cycle wherein the arene activating metal, M’ (Scheme 2), functions catalytically by exchanging from the product to a new starting arene.…”

Section: Introductionmentioning

confidence: 99%

Cation−π Interactions in the Benzylic Arylation of Toluenes with Bimetallic Catalysts

Sha

Tcyrulnikov

et al. 2018

J. Am. Chem. Soc.

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A method to directly arylate toluene derivatives with aryl bromides to generate diarylmethanes, which are important building blocks in drug discovery, is described. In this method, KN(SiMe) in combination with a (NIXANTPHOS)Pd catalyst accomplished the deprotonative activation of toluene derivatives to permit cross-coupling with aryl bromides. Good to excellent yields are obtained with a range of electron-rich to neutral aryl bromides. Both electron-rich and electron-poor toluene derivatives are well tolerated, and even 2-chlorotoluene performs well, providing a platform for introduction of additional functionalization. This discovery hinges on the use of a main group metal to activate toluene for deprotonation by means of a cation-π interaction, which is secured by a bimetallic K(NIXANTPHOS)Pd assembly. Mechanistic and computational studies support acidification of toluene derivatives by the K-cation- π interaction, which may prove pertinent in the development of other, new reaction systems.

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“…Recently, transition‐metal‐catalyzed allylic alkylation reactions of unstabilized benzylic nucleophiles have attracted interest because of their applications in the synthesis of a broad diversity of complex molecules . Pioneering works from the groups of Trost and Walsh have led to impressive palladium‐catalyzed processes for asymmetric allylic alkylation with 2‐methylpyridine derivatives (p K a ≈34) and toluene derivatives (p K a ≈44), respectively. In these studies, elegant strategies have been developed that involve the addition of activating agents to stabilize the resulting anionic charge.…”

Section: Figurementioning

confidence: 99%

Enantioselective Iridium‐Catalyzed Allylic Substitution with 2‐Methylpyridines

Liu

You

2017

Angewandte Chemie

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An enantioselective iridium‐catalyzed allylic substitution with a set of highly unstabilized nucleophiles generated in situ from 2‐methylpyridines is described. Enantioenriched 2‐substituted pyridines, which are frequently encountered in natural products and pharmaceuticals, could be easily constructed by this simple method in good yields and excellent enantioselectivity. The synthetic utility of the pyridine products is demonstrated through the synthesis of a key intermediate of a reported Na+/H+ exchanger inhibitor and the total synthesis of (−)‐lycopladine A.

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Palladium‐Catalyzed Asymmetric Allylic Alkylations with Toluene Derivatives as Pronucleophiles

Cited by 68 publications

References 48 publications

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications

Cation−π Interactions in the Benzylic Arylation of Toluenes with Bimetallic Catalysts

Enantioselective Iridium‐Catalyzed Allylic Substitution with 2‐Methylpyridines

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