Pd-catalyzed asymmetric allylic substitution cascade using α-(pyridin-1-yl)-acetamides formed<i>in situ</i>as nucleophiles

Yao, Kun; Yuan, Quan; Qu, Xingxin; Liu, Yangang; Liu, Delong; Zhang, Wanbin

doi:10.1039/c8sc04626c

Cited by 25 publications

(7 citation statements)

References 72 publications

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“…Chiral piperidine-containing amino acid derivatives were obtained with high yields and enantioselectivities (up to 96% ee ; Scheme 65 ). 210 …”

Section: Asymmetric Allylic Substitutionmentioning

confidence: 99%

“…Chiral piperidine-containing amino acid derivatives were obtained with high yields and enantioselectivities (up to 96% ee; Scheme 65). 210 Phosferrox ligands, in which the phenyl group of the PHOX ligand had been replaced by a ferrocene moiety, recently found new applications in the Pd-catalyzed AAA. For instance, Sarlah's group developed a one pot protocol for the dearomative syn-1,4-diamination of naphthalene that involves a visible-light mediated [4+2]-photocycloaddition followed by a Pd-catalyzed allylic amination (Scheme 66a).…”

Section: Malonates Related Stabilized C-nucleophiles and O- S- N- And...mentioning

confidence: 99%

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

Pàmies

Margalef

Cañellas³

et al. 2021

Chem. Rev.

369

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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“…Chiral piperidine-containing amino acid derivatives were obtained with high yields and enantioselectivities (up to 96% ee ; Scheme 65 ). 210 …”

Section: Asymmetric Allylic Substitutionmentioning

confidence: 99%

Section: Malonates Related Stabilized C-nucleophiles and O- S- N- And...mentioning

confidence: 99%

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

Pàmies

Margalef

Cañellas³

et al. 2021

Chem. Rev.

369

202

View full text Add to dashboard Cite

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“…Notable unsymmetrical ligands applied in AAS include PHOX (Fig. 1), 8 IndoPHOX, 9 RuPHOX, 10 Phosferrox, 11 Josiphos, 12 FerroNPS, 13 etc . Despite remarkable advances in chiral ligand design, some of the ligands are still rarely tolerated by a wide range of substrates, and each type of substrate often requires a particular ligand to obtain excellent enantioselectivity.…”

Section: Introductionmentioning

confidence: 99%

New P,N_sp3ligands for palladium-catalyzed asymmetric allylic substitutions

Hou

Wei

et al. 2023

Org. Biomol. Chem.

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“…Allylic substrates bearing activated leaving groups, such as carboxylates (acetates), − carbonates, ,− phosphates, and halides, as well as allylic molecules having trichloroacetimidate, trimethylsilyl, carbamates, and ureas exhibit high reactivity in AAA reactions. Nonetheless, allylic alcohols, ,,− ethers, , amines, ,,− and C–H bonds were recently applied directly as simple alternative allylic sources; however, an AAA reaction with such stable allylic sources has been developed almost exclusively by using easy-to-handle precious-metal-based catalysts, such as palladium, rhodium, and iridium complexes. In this context, some of us recently reported the AAA reaction of β-ketoesters with allylic alcohols to construct quaternary chiral centers mediated by a nonprecious nickel complex bearing chiral diphosphine ligand .…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Allylic Alkylation of β-Ketoesters via C–N Bond Cleavage of N-Allyl-N-methylaniline Derivatives Catalyzed by a Nickel–Diphosphine System

et al. 2020

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Nickel complexes bearing chiral diphosphine ligands, such as (S)-Tol-MeO-BIPHEP and (S)-H 8 -BINAP, serve as efficient catalysts for asymmetric allylic alkylation (AAA) of β-ketoesters using allylic amines as allyl sources. The reactions proceed with high catalytic activity and high enantioselectivity. N-Methyl-N-phenyl allylic amines were indispensable to achieve the high catalytic activity and high enantioselectivity, and to expand the substrate scope to 5-and 7-membered β-ketoesters, whose nickel-catalyzed AAA with allylic alcohols results in low enantioselectivity. On the basis of the kinetics using a catalyst system made of Ni(cod) 2 and (S)-Tol-MeO-BIPHEP, and DFT calculations for the reaction pathway of the AAA reaction mediated by an isolated olefin-coordinated nickel-DPPF complex 4b, we propose a mechanism where protonation of the nitrogen atom of the coordinating allylic amine by β-ketoester is key to cleaving the C-N bond and delivering a cationic π-allyl nickel(II) intermediate. ASSOCIATED CONTENT Supporting InformationDetails of experimental procedures, optimization of reaction conditions, kinetic studies, NMR spectra, HPLC chart for all new compounds, and Cartesian coordinates of DFT-computed structures (PDF) were included in a Supporting Information. X-ray crystallographic data for complex 4b (CIF).

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Pd-catalyzed asymmetric allylic substitution cascade using α-(pyridin-1-yl)-acetamides formedin situas nucleophiles

Abstract: A Pd-catalyzed asymmetric allylic substitution cascade reaction, using α-(pyridin-1-yl)-acetamides (formed in situ) as nucleophiles, has been developed.

Cited by 25 publications

References 72 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

New P,N_sp3ligands for palladium-catalyzed asymmetric allylic substitutions

Asymmetric Allylic Alkylation of β-Ketoesters via C–N Bond Cleavage of N-Allyl-N-methylaniline Derivatives Catalyzed by a Nickel–Diphosphine System

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Pd-catalyzed asymmetric allylic substitution cascade using α-(pyridin-1-yl)-acetamides formedin situas nucleophiles

Abstract: A Pd-catalyzed asymmetric allylic substitution cascade reaction, using α-(pyridin-1-yl)-acetamides (formed in situ) as nucleophiles, has been developed.

Cited by 25 publications

References 72 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

New P,Nsp3ligands for palladium-catalyzed asymmetric allylic substitutions

Asymmetric Allylic Alkylation of β-Ketoesters via C–N Bond Cleavage of N-Allyl-N-methylaniline Derivatives Catalyzed by a Nickel–Diphosphine System

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New P,N_sp3ligands for palladium-catalyzed asymmetric allylic substitutions