Synthesis of original phosphine-sulfoxide ligands for asymmetric allylic alkylation

Alvarado-Beltrán, Isabel; González, Martha Letícia Gaeta; Escudié, Yannick; Maerten, Eddy; Saffon‐Merceron, Nathalie; Fabing, Isabelle; Toledano, Cecilio Álvarez; Baceiredo, Antoine

doi:10.1016/j.tet.2016.02.012

Cited by 9 publications

(4 citation statements)

References 72 publications

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“…Another strategy to tackle the problem of controlling the configuration of the coordinated thioether group is based on the use of chiral sulfoxides or sulfonamides as structural elements instead of thioether groups (Figure ). ,− …”

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.

329

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.

329

202

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“…Maerten, Baceiredo, and co-workers synthesized another type of phosphorus-containing sulfoxide ligands containing both phosphine diamide and sulfoxide moieties. The enantioselectivity of the title reaction was generally moderate (37–61% ee), with the best being for ligand 81a (Figure ), thus having only one stereogenic center on the sulfinyl sulfur atom (conversion 73% and 74% ee) …”

Section: Sulfoxidesmentioning

confidence: 99%

“…The enantioselectivity of the title reaction was generally moderate (37−61% ee), with the best being for ligand 81a (Figure 28), thus having only one stereogenic center on the sulfinyl sulfur atom (conversion 73% and 74% ee). 53 Toru and co-workers for the first time reported synthesis of chiral 1-phosphino-1′-sulfinylferrocenes 82 (Figure 29). These spatially and electronically varied sulfoxides were used as chiral ligands in the allylic alkylation of acetate 71 by dimethyl malonate (cf.…”

Section: Allylic Substitutionmentioning

confidence: 99%

Chiral Organosulfur Ligands/Catalysts with a Stereogenic Sulfur Atom: Applications in Asymmetric Synthesis

et al. 2017

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Asymmetric synthesis, in which chiral organocatalysts or metal complexes with chiral ligands are used, has become the most valuable methodology for the preparation of enantiomerically pure organic compounds. Among such catalysts/ligands, a growing number constitute various organosulfur compounds. This Review provides comprehensive and critical information on the plethora of sulfur-based chiral ligands and organocatalysts used in asymmetric synthesis, which have been published within the last 15 years. However, it is confined to the presentation of only those chiral catalysts/ligands that possess a stereogenic sulfur atom and includes sulfoxides, sulfinamides, N-sulfinyl ureas, sulfoximines, and some related S-chiral derivatives.

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“…In 2016, Maerten, Baceiredo, and co-workers synthesized chiral phosphine-sulfoxide ligands in Pd-catalyzed asymmetric allylic alkylation reactions (Scheme 5 ). 27 The chiral ligand L7 facilitated an asymmetric allylation reaction using (–)-1,3-diphenylallyl acetate and dimethyl malonate. In the presence of 2 mol% of ligand L7 , the reaction was essentially complete after 12 h, giving the corresponding alkylated compound in 59% ee.…”

Section: Chiral Sulfoxides As Ligands In Metal-catalyzed Asymmetric C...mentioning

confidence: 99%

Recent Advances for Chiral Sulfoxides in Asymmetric Catalysis

2022

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Chiral sulfoxide is considered to be an ideal candidate ligand for transition metal-catalyzed asymmetric reactions due to its easiness of synthesis, stability, and exceptional S-stereological orientation control. This paper reviews the different types of asymmetrical reactions with chiral sulfoxide ligands in recent years, as well as a discussion of efficient methods for the preparation of some enantiomerically pure sulfoxides.

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Synthesis of original phosphine-sulfoxide ligands for asymmetric allylic alkylation

Cited by 9 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

Chiral Organosulfur Ligands/Catalysts with a Stereogenic Sulfur Atom: Applications in Asymmetric Synthesis

Recent Advances for Chiral Sulfoxides in Asymmetric Catalysis

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