Synthesis of phosphorylated sulfoximines and sulfinamides and their application as ligands in asymmetric metal catalysis

Benetskiy, Eduard B.; Bolm, Carsten

doi:10.1016/j.tetasy.2011.02.005

Cited by 46 publications

(8 citation statements)

References 35 publications

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“…Among the monodentate P-donor ligands developed since 2008 for Pd-catalyzed asymmetric allylic alkylation (AAA), diamidophosphites − and phosphoramidites − were found to provide higher enantioselectivities than their phosphite, , phosphinite, and phosphine − counterparts. Scheme collects the most representative families of monodentate P-donor ligands evaluated in the allylic alkylation of rac -1,3-diphenylallyl acetate as substrate with dimethyl malonate as nucleophile.…”

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.

362

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.

362

202

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“…Hence, optically active compounds based on 2 have been utilized in the synthesis of pseudopeptides [ 20 – 24 ], and they have found widespread application in auxiliary-assisted diastereoselective transformations or as chiral ligands in enantioselective metal catalysis [ 25 – 33 ]. With respect to the latter field we have recently demonstrated that various ligands bearing a sulfonimidoyl moiety lead to excellent stereoselectivities in transition metal-catalyzed hydrogenations and carbon–carbon bond formations [ 34 – 36 ].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of chiral sulfoximine-based thioureas and their application in asymmetric organocatalysis

Frings¹,

Thomé²,

Bolm³

2012

Beilstein J. Org. Chem.

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SummaryFor the first time, chiral sulfoximine derivatives have been applied as asymmetric organocatalysts. In combination with a thiourea-type backbone the sulfonimidoyl moiety leads to organocatalysts showing good reactivity in the catalytic desymmetrization of a cyclic meso-anhydride and moderate enantioselectivity in the catalytic asymmetric Biginelli reaction. Straightforward synthetic routes provide the newly designed thiourea-sulfoximine catalysts in high overall yields without affecting the stereohomogeneity of the sulfur-containing core fragment.

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“…[b] The conversion of substrate 9 and enantiomeric excess of 10 b were determined by HPLC (Kromasil 5‐CelluCoat, C 6 H 14 / i PrOH=99/1, 0.6 mL/min, 254 nm, t ( R )=18.6 min, t ( S )=20.7 min). [c] The absolute configuration was assigned by comparison of the HPLC retention times reported in the literature …”

Section: Resultsmentioning

confidence: 99%

(S)-2-[(N-arylamino)methyl]pyrrolidines-Based PhosphoramiditeP,N-Ligand Library for Asymmetric Metal-Catalyzed Allylic Substitution and Conjugate 1,4-Addition

et al. 2016

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A library of easy‐to‐prepare and modular chiral P,N‐phosphoramidites based on [1,1′‐biaryl]‐2,2′‐diols and C1‐symmetric 1,2‐diamines has been designed and developed. The structures of the novel ligands have been elucidated by means of 2D‐NMR and confirmed in the solid state by X‐ray diffraction analysis. Stereoselectors of this type exhibited high enantioselectivities in Pd‐catalyzed allylic substitution reactions of (E)‐1,3‐diphenylallyl acetate with NaSO2pTol (up to 91 % ee), CH2(CO2Me)2 (up to 89 % ee), (C3H7)2NH (up to 94 % ee) and (EtO)2P(O)CH2NH2 as a novel nucleophile (up to 98 % ee). Ee values of up to 88 % and 72 % have been obtained in the Pd‐catalyzed desymmetrization of N,N′‐ditosyl‐meso‐cyclopent‐4‐ene‐1,3‐diol biscarbamate and in the Cu‐catalyzed 1,4‐conjugate addition of diethylzinc to chalcone, respectively. The reactions of P,N‐bidentate ligands with [Pd(Cod)Cl2] at molar ratios of L/M=1 and 2 have been studied using 1H, 13C, 13C‐1H HSQC, 13C‐1H HMBC, 1H‐1H COSY, 1H‐1H ROESY, DOSY and 31P NMR spectroscopy as well as HR ESI mass spectrometry.

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Synthesis of phosphorylated sulfoximines and sulfinamides and their application as ligands in asymmetric metal catalysis

Cited by 46 publications

References 35 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

Synthesis of chiral sulfoximine-based thioureas and their application in asymmetric organocatalysis

(S)-2-[(N-arylamino)methyl]pyrrolidines-Based PhosphoramiditeP,N-Ligand Library for Asymmetric Metal-Catalyzed Allylic Substitution and Conjugate 1,4-Addition

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