Asymmetric Baylis Hillman Reaction Research Articles

β-Isocupreidine–hexafluoroisopropyl acrylate method for asymmetric Baylis–Hillman reactions

Key features of the β-isocupreidine (β-ICD)-catalyzed asymmetric Baylis–Hillman reaction of aldehydes with 1,1,1,3,3,3-hexafluoroisopropyl acrylate (HFIPA) are presented. In addition, an improved method using azeotropically dried β-ICD is described.

Ferrocenylphosphines as New Catalysts for Baylis−Hillman Reactions

[reaction: see text] Readily available ferrocenyldialkylphosphines are effective air-stable catalysts for Baylis-Hillman reaction between aldehydes and acrylates, affording the corresponding adducts in high yields and short reaction times. A set of readily accessible planar chiral ferrocenyldialkylphosphines have been tested in asymmetric Baylis-Hillman reactions. The best enantioselectivities were obtained using Mandyphos as chiral catalyst (up to 65% ee).

Asymmetric Baylis–Hillman reactions using ( R)-4-(3-hydroxy-4,4-dimethyl-2-oxopyrrolidin-1-yl) benzoic acid acrylate derivatives in solution and on solid support

The influence of several variables on the course of the Baylis–Hillman reaction between the ( R)-4-(3-hydroxy-4,4-dimethyl-2-oxopyrrolidin-1-yl) benzoic acid acrylate derivatives ( R)- 2 and ( R)- 3 and aromatic aldehydes has been investigated both in solution and on solid support: these resulted in comparable results with the formation of adducts in high yield and moderate selectivity.

(6R,7aS)-1,3,5,6,7,7a-Hexahydro-3-(2-hydroxyphenyl)-1,1-diphenylpyrrolo[1,2-c][1,3]oxazol-6-ol

The molecule of the title compound, C24H23NO3, consists of five rings, of which the pyrrole ring and oxazole ring are not planar. The compound was designed as a catalyst of the asymmetric Baylis–Hillman reaction, but it only has poor catalysis activity. According to the crystal structure analysis, this might be caused by steric hindrance due to the intramolecular O—H⋯N hydrogen bond. In the crystal structure, the mol­ecules are connected by O—H⋯O and C—H⋯O hydrogen bonds, forming chains along [010]. The chains further interact through C—H⋯O hydrogen bonds, stacking along [100]. In the third direction [001], there is only weak interaction, which explains the crystal habit of a thin plate.

First Application of Chiral Ionic Liquids in Asymmetric Baylis—Hillman Reaction.

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Development of Bis‐thiourea‐Type Organocatalyst for Asymmetric Baylis—Hillman Reaction.

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The Chiral Diamine Mediated Asymmetric Baylis–Hillman Reaction

AbstractA chiral diamine, easily prepared from proline, is an effective, asymmetric organic catalyst for the Baylis–Hillman reaction of aldehydes and methyl vinyl ketone, affording adducts with enantioselectivities up to 75%.

First application of chiral ionic liquids in asymmetric Baylis–Hillman reaction

The first example of the use of chiral ionic liquids as reaction media in the asymmetric Baylis–Hillman reaction was described using N-alkyl- N-methylephedrinium salts. Good yields and significant enantiomeric excesses were obtained.

The Asymmetric Baylis—Hillman Reaction

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Development of bis-thiourea-type organocatalyst for asymmetric Baylis–Hillman reaction

A new chiral bis-thiourea-type organocatalyst 2 developed for the Baylis–Hillman reaction provided a drastic rate enhancement. Allylic alcohols were obtained with up to 90% ee in the case of cyclohexanecarboxaldehyde (4i).

Metal‐Free Bifunctional Catalysis of the Asymmetric Baylis—Hillman Reaction.

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Metal-Free Bifunctional Catalysis of the Asymmetric Baylis-Hillman Reaction

The Sharpless ligand (DHQD)2AQN acts a bifunctional catalyst for the asymmetric Baylis-Hillman reaction. Enantioselectivities up to 77% have been observed.

β‐Isocupreidine‐Catalyzed Asymmetric Baylis—Hillman Reaction of Imines.

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Chiral Lewis Acid Catalyzed Asymmetric Baylis—Hillman Reactions.

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Catalytic, Asymmetric Baylis—Hillman Reaction of Imines with Methyl Vinyl Ketone and Methyl Acrylate.

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An Exploration of Asymmetric Baylis—Hillman Reactions Catalyzed by Quinidine‐Derived Chiral Amines.

Abstract We utilized a reported quinidine-derived chiral amine 1 to catalyze the asymmetric Baylis–Hillman reaction of aldehydes with methyl vinyl ketone. The enantioselectivities increase and in some cases, the absolute configuration of the Baylis–Hillman adducts can be inverted by the use of proline or lithium salt additives. The highest ee achieved is 49% with S configuration at the newly formed stereogenic centre. When using chiral amine 1 to catalyze the asymmetric Baylis–Hillman reaction of aldehydes with (α)-naphthyl acrylate, ee as high as 92% can be achieved.

Diastereoselective Baylis-Hillmanreaction: Use of Sugar Derived Aldehydes as Chiral Electrophiles

The asymmetric Baylis-Hillman reaction of sugar-derived aldehydes as chiral electrophiles with an activated olefin in dioxane: water (1:1) with 36-86% de and in good yields is described.

Chiral Lewis acid-catalyzed asymmetric Baylis-Hillman reactions.

An effective chiral Lewis acid-catalyzed asymmetric Baylis-Hillman reaction is described. Good to high enantioselectivities were obtained using 3 mol % chiral catalyst. Novel camphor-derived dimerized ligands were prepared from the condensation of (+)-ketopinic acid with the corresponding diamines and hydrazine under acidic conditions. When alpha-naphthyl acrylate was used as a Michael acceptor, the reaction is complete within 20 min with high stereoselectivity and in reasonable chemical yields.

Catalytic, asymmetric Baylis-Hillman reaction of imines with methyl vinyl ketone and methyl acrylate.

Catalytic, asymmetric Baylis-Hillman reaction of imines with methyl vinyl ketone and methyl acrylate.

An exploration of asymmetric Baylis–Hillman reactions catalyzed by quinidine-derived chiral amines

We utilized a reported quinidine-derived chiral amine 1 to catalyze the asymmetric Baylis–Hillman reaction of aldehydes with methyl vinyl ketone. The enantioselectivities increase and in some cases, the absolute configuration of the Baylis–Hillman adducts can be inverted by the use of proline or lithium salt additives. The highest ee achieved is 49% with S configuration at the newly formed stereogenic centre. When using chiral amine 1 to catalyze the asymmetric Baylis–Hillman reaction of aldehydes with (α)-naphthyl acrylate, ee as high as 92% can be achieved.