Enantioselective oxidation of sulfides with hydrogen peroxide catalyzed by vanadium complex of sterically hindered chiral Schiff bases

Jeong, Yong‐Chul; Choi, Soo‐Jin; Hwang, Yao Dong; Ahn, Kwang‐Hyun

doi:10.1016/j.tetlet.2004.10.070

Cited by 68 publications

(27 citation statements)

References 36 publications

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“…This trend has been observed in other investigations, 66,72,77,93 although to a lesser extent, indicating that the influence of the ligand is greater than that of the substituent on the aromatic ring of the sulfide. Interestingly, the report by Barbarini et al employing a polymer supported ligand showed the opposite trend.…”

Section: Scheme 32supporting

confidence: 81%

Synthesis of enantioenriched sulfoxides

O’Mahony¹,

Kelly²,

Lawrence³

et al. 2011

Arkivoc

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This review discusses strategies for the asymmetric synthesis of sulfoxides, compounds with many applications in stereoselective synthesis and in some cases with pharmaceutical application. The review describes asymmetric oxidation, including metal catalyzed and nonmetal and biological oxidation processes, in addition to synthetic approaches via nucleophilic substitution of appropriately substituted precursors. Kinetic resolution in oxidation of sulfoxides to the analogous sulfones is also discussed; in certain instances, access to enantioenriched sulfoxides can be achieved via a combination of asymmetric sulfide oxidation and complementary kinetic resolution in sulfoxide oxidation.

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Section: Scheme 32supporting

confidence: 81%

Synthesis of enantioenriched sulfoxides

O’Mahony¹,

Kelly²,

Lawrence³

et al. 2011

Arkivoc

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“…[19,23,26] The studies showed that the vanadiumbased catalysts of chiral Schiff bases with the substituent possessing an additional chiral element on the 3-position of the salicylidenyl moiety displayed apparently higher activity and enantioselectivity in asymmetric oxidation of sulfides. [20] We systematically studied the influence of the substituents, ortho to the phenolic hydroxyl group of a chiral Schiff base ligand, on activity and enantioselectivity of the vanadium-based catalysts for asymmetric oxidation of prochiral sulfides. A series of chiral Schiff bases, 2-(N-3-aryl-5-tert-butylsalicylidene)aminoalcohols (L 1 -L 5 ) and 2-(N-3-aryl-5-bromosalicylidene)aminoalcohols (L 6 and L 7 ), were prepared.…”

Section: Introductionmentioning

confidence: 99%

Influence of substituents in the salicylaldehyde‐derived Schiff bases on vanadium‐catalyzed asymmetric oxidation of sulfides

Liu

Wang

et al. 2008

Applied Organom Chemis

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A series of chiral Schiff bases (L 1 -L 5 ) with different substituents in the salicylidenyl unit were prepared from condensation of 3-aryl-5-tert-butylsalicylaldehyde derivatives and optically active amino alcohols. Bromination of 3-phenyl-5-tertbutylsalicylaldehyde gave an unexpected product 3-(4-bromophenyl)-5-bromosalicylaldehyde, from which the corresponding Schiff base ligands L 6 and L 7 , derived from (S)-valinol and (S)-tert-leucinol, respectively, were prepared. Ligands L 1 -L 7 were applied to the vanadium-catalyzed asymmetric oxidation of aryl methyl sulfides. Under the optimal conditions, the oxidation of the thioanisole with H 2 O 2 as oxidant in CH 2 Cl 2 catalyzed by VO(acac) 2 -L 1 -L 7 gives good yields (74-83%) with moderate enantioselectivity (58-77% ee). Ligand L 7 , containing a 4-bromophenyl group on the 3-position and a Br atom on the 5-position of the salicylidenyl moiety, displays an 80-90% ee for vanadium-catalyzed oxidation of methyl 4-bromophenyl sulfide and methyl 2-naphthyl sulfide.

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“…[5] Peroxido-vanadium complexes are capable of the single oxidation of organic sulfides to sulfoxides with little double oxidation product (sulfone). [1,6,7] A number of catalysts have been presented in the literature [3,[8][9][10][11] to be competent with respect to sulfide oxidation and in some cases to be stereoselective. To date the best peroxido vanadium-based catalyst is K[VO(O 2 )-Hheida], showing the highest rates of sulfide oxidation of any reported catalyst for bromide and organic sulfide oxidation.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Analysis of Nucleophilic Substrates Oxidation by Functional Models of Vanadium‐Dependent Haloperoxidases: A Density Functional Theory Study

et al. 2007

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Density functional theory has been used to investigate the structural, electronic, and reactivity properties of an established functional model for vanadium‐dependent haloperoxidases, K[VO(O2)Hheida] (Hheida2– = 2,2′‐[(2‐hydroxyethyl)imino]diacetate). Possible solution species were determined on the basis of potential exogenous donors present under the conditions necessary for reactivity. The energetically favored solution‐state species is a 1:1 complex of Hheida and vanadium with a coordinated hydroxyethyl donor trans to the vanadium–oxido bond which is in agreement with the reported solid‐state structure for K[VO(O2)Hheida]. Transition states of the oxidation reaction were located for four substrates: chloride, bromide, iodide, and dimethyl sulfide. The role of protonation and its effects on reactivity were examined for each substrate. Protonation of the peroxido moiety leads to a significant drop in the activation barrier for oxidation. In contrast no transition states could be located for an oxido‐transfer process involving the oxido ligand. Barriers of activation calculated for halide oxidation were similar, providing support to the hypothesis that the pKa of the halide in acetonitrile is responsible for the decrease in reactivity between I–, Br–, and Cl–. The results presented herein provide a mechanistic correlation between a functional model and the enzyme, making K[VO(O2)Hheida] a “complete” functional model for vanadium‐dependent haloperoxidase.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

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Enantioselective oxidation of sulfides with hydrogen peroxide catalyzed by vanadium complex of sterically hindered chiral Schiff bases

Cited by 68 publications

References 36 publications

Synthesis of enantioenriched sulfoxides

Synthesis of enantioenriched sulfoxides

Influence of substituents in the salicylaldehyde‐derived Schiff bases on vanadium‐catalyzed asymmetric oxidation of sulfides

Mechanistic Analysis of Nucleophilic Substrates Oxidation by Functional Models of Vanadium‐Dependent Haloperoxidases: A Density Functional Theory Study

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