Stoichiometric asymmetric oxidation with hydrogen peroxide activated by a chiral phosphoryl chloride

Berkessel, Albrecht; Frauenkron, Matthias

doi:10.1016/0957-4166(96)00061-4

Cited by 9 publications

(4 citation statements)

References 3 publications

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“…[148][149][150][151] Another example of epoxidation of olefins using a stoichiometric amount of a chiral reagent (R)-79 generated from phosphoryl chloride and (R)-BINOL 1 has been described by Berkessel et al (Scheme 36). 152 Only low enantiomeric excesses were obtained (maximum 22% ee) (Table 9). A possible mechanistic interpretation involving a chiral (RO) 2 P(O)-OOH intermediate has been suggested.…”

Section: Epoxidation Of Olefinsmentioning

confidence: 99%

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BINOL: A Versatile Chiral Reagent

Brunel¹

2005

Chem. Rev.

931

367

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Section: Epoxidation Of Olefinsmentioning

confidence: 99%

“…Another example of epoxidation of olefins using a stoichiometric amount of a chiral reagent ( R )- 79 generated from phosphoryl chloride and ( R )-BINOL 1 has been described by Berkessel et al (Scheme ) . Only low enantiomeric excesses were obtained (maximum 22% ee) (Table ).…”

Section: 2 Enantioselective Oxidation Reactions321 Epoxidation Of Ole...mentioning

confidence: 99%

BINOL: A Versatile Chiral Reagent

Brunel¹

2005

Chem. Rev.

931

367

View full text Add to dashboard Cite

“…Another example of epoxidation of olefins, using a stoichiometric amount of a chiral reagent ( R )- 79 generated from phosphoryl chloride and ( R )-BINOL 1 , has been described by Berkessel et al (Scheme ) 40 …”

Section: 2 Enantioselective Oxidation Reactions321 Epoxidation Of Ole...mentioning

confidence: 99%

“…160 Another example of epoxidation of olefins, using a stoichiometric amount of a chiral reagent (R)-79 generated from phosphoryl chloride and (R)-BINOL 1, has been described by Berkessel et al (Scheme 40). 161 Only low enantiomeric excesses were obtained (maximum 22% ee) (Table 10). A possible mechanistic interpretation involving a chiral (RO) 2 P(O)-OOH intermediate has been suggested.…”

Section: Epoxidation Of Olefinsmentioning

confidence: 99%

Update 1 of: BINOL: A Versatile Chiral Reagent

Brunel¹

2007

Chem. Rev.

225

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Chiral Brønsted Acid Catalyzed Asymmetric Baeyer–Villiger Reaction of 3‐Substituted Cyclobutanones by Using Aqueous H₂O₂

Wang

Zhang

et al. 2008

Angewandte Chemie

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The Baeyer-Villiger (BV) reaction represents one of the most well-known and widely applied reactions in organic synthesis.[1] Although more than one century has gone by since its discovery in 1899, [2] the BV reaction is still far from being fully developed. Although the use of aqueous hydrogen peroxide as an environmentally benign oxidant has been a long-sought goal for the BV reaction, [3] significant efforts still need to be made in the area of enantioselective BV reactions. Since the pioneering work by the groups of Strukul [4a] and Bolm [4b] in 1994, a number of chiral metal complexes or organic molecules have been developed as promoters or catalysts for the BV reaction of various ketones, [5] but there are only a few cases in which the catalysts are used in combination with aqueous hydrogen peroxide as the oxidant. [4a, 6] Although very impressive results have been achieved for the catalytic enantioselective BV reaction in the work reported by the groups of Bolm, [4b, 7] Katsuki, [8] and Murahashi, [6b] the development of the reaction is slow when compared to the rapid development of other catalytic asymmetric transformations. [9] To the best of our knowledge only a few catalyst systems afford products from the BV oxidation of 3-substituted cyclobutanones in more than 80 % ee, [8b, c] despite the fact that some enzymatic systems show excellent enantiocontrol in the reaction.[10] Herein, we communicate our preliminary results on the first example of the enantioselective BV oxidation of 3-substituted cyclobutanones catalyzed by a chiral Brønsted acid and 30 % aqueous H 2 O 2 as the oxidant to afford the corresponding g-lactones in excellent yields and up to 93 % ee.The research was inspired by the fact that BV reaction is accelerated by strong Bønsted acids, and that the activity of the peracid is dependent on the acidity of the Bønsted acid. [3,11] It was reported that the use of a stoichiometric amount of the chiral organic hydroperoxide {(4R,5R)-5-[(hydroperoxydiphenyl)methyl]-2,2-dimethyl-1,3-dioxolan-4-yl}diphenylmethanol (TADOOH) afforded enantioselectivities of 55 % in the asymmetric BV oxidation of bicyclo-[4.2.0]octanone.[12] The difficulty in developing a catalytic enantioselective version of this reaction may be ascribed to the weak acidity of the hydroxy groups in the a,a,a',a'-tetraaryl-1,3-dioxolan-4,5-dimethanol (TADDOL) molecule. Chiral phosphoric acids derived from 2,2'-dihydroxy-1,1'-binapthyl (binol) are recognized as Brønsted acids that are widely used as catalysts in a variety of asymmetric reactions with high catalytic activity and excellent enantioselectivity. [13] A preliminary examination of binol-derived phosphoric acid 1 a (10 mol %) in the BV oxidation of 3-phenylcyclobutanone (2 a) with 1.5 equivalents of aqueous H 2 O 2 (30 %) in CHCl 3 at room temperature afforded 3-phenyl-g-butyrolactone (3 a) with good catalytic activity (12 h, 99 % yield), albeit very poor enantioselectivity (ca. 2 % ee). Notably, a reaction did not occur in the absence of 1 a under otherwise identical...

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Stoichiometric asymmetric oxidation with hydrogen peroxide activated by a chiral phosphoryl chloride

Cited by 9 publications

References 3 publications

BINOL: A Versatile Chiral Reagent

BINOL: A Versatile Chiral Reagent

Update 1 of: BINOL: A Versatile Chiral Reagent

Chiral Brønsted Acid Catalyzed Asymmetric Baeyer–Villiger Reaction of 3‐Substituted Cyclobutanones by Using Aqueous H₂O₂

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Stoichiometric asymmetric oxidation with hydrogen peroxide activated by a chiral phosphoryl chloride

Cited by 9 publications

References 3 publications

BINOL: A Versatile Chiral Reagent

BINOL: A Versatile Chiral Reagent

Update 1 of: BINOL: A Versatile Chiral Reagent

Chiral Brønsted Acid Catalyzed Asymmetric Baeyer–Villiger Reaction of 3‐Substituted Cyclobutanones by Using Aqueous H2O2

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Chiral Brønsted Acid Catalyzed Asymmetric Baeyer–Villiger Reaction of 3‐Substituted Cyclobutanones by Using Aqueous H₂O₂