Increased Structural Complexity Leads to Higher Activity:  Peptides as Efficient and Versatile Catalysts for Asymmetric Aldol Reactions

Krattiger, Philipp; Kovàsy, Roman; Revell, Jefferson D.; Ivan, Stanislav; Wennemers, Helma

doi:10.1021/ol0500259

Cited by 266 publications

(131 citation statements)

References 15 publications

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“…Finally, proline-derived small peptides can frequently serve as efficient chiral organocatalysts. [132][133][134][135][136][137] Although the peptide-series catalysts usually have molecular weights about five times as large as proline itself, they work well even in THF/water mixed solvent system to give excellent enantioselectivities of up to 96% ee (Scheme 39). A surprising result in this system is their reversed regioselectivity with regard to the methyl group: the reaction took place preferentially at the methyl group of hydroxyacetone to give the 1,4-diol products.…”

Section: 115mentioning

confidence: 99%

Organocatalytic Asymmetric Synthesis Using Proline and Related Molecules. Part 1

Kotsuki¹,

Ikishima²,

Okuyama³

2008

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-Organocatalytic asymmetric synthesis has been extensively studied and several important procedures for preparing optically active organic compounds have been developed. Research in this area has progressed rapidly in the last ten years. This review addresses the most significant advances in asymmetric synthesis using proline and related chiral organocatalysts mainly focusing on aldol reactions from the viewpoint of synthetic interests. This includes (1) proline-catalyzed aldol reactions, (2) proline-related chiral catalysts, and (3) other types of amino acid catalysts.

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Section: 115mentioning

confidence: 99%

Organocatalytic Asymmetric Synthesis Using Proline and Related Molecules. Part 1

Kotsuki¹,

Ikishima²,

Okuyama³

2008

HETEROCYCLES

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“…131 Finally, proline-derived small peptides can frequently serve as efficient chiral organocatalysts. [132][133][134][135][136][137] Although the peptide-series catalysts usually have molecular weights about five times as large as proline itself, they work well even in THF/water mixed solvent system to give excellent enantioselectivities of up to 96% ee (Scheme 39). 134 A surprising result in this system is their reversed regioselectivity with regard to the methyl group: the reaction took place preferentially at the methyl group of hydroxyacetone to give the 1,4-diol products.…”

Section: Prolinamide Catalystsmentioning

confidence: 99%

Organocatalytic Asymmetric Synthesis Using Proline and Related Molecules. Part 2.

Kotsuki¹,

Ikishima²,

Okuyama³

2008

HETEROCYCLES

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“…15 Solution phase studies revealed that, particularly with 1, 1 mol % is sufficient to obtain aldol products in up to quantitative yields and up to 90% enantiomeric excess. Compared to the rigid, small organocatalyst proline, 1 is more than 30-fold more active with either comparable or higher selectivity.…”

Section: Introductionmentioning

confidence: 99%

Solid‐supported and pegylated H–Pro–Pro–Asp–NHR as catalysts for asymmetric aldol reactions

et al. 2005

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H-Pro-Pro-Asp-NH2 is a highly active and selective catalyst for asymmetric aldol reactions. Here, the versatility of H-Pro-Pro-Asp-NH2 has been further improved by immobilization on a solid support and functionalization with a short polyethylene glycol linker at the C-terminus. The development, synthesis, and the catalytic properties in aldol reactions of H-Pro-Pro-Asp-resin and H-Pro-Pro-Asp-Ahx-NH(CH2CH2O)3CH3 are described. For the solid-supported catalyst, TentaGel with a loading of 0.1-0.2 mmol g(-1) proved to be the optimal support. The solid-supported catalyst can be recycled at least three times without a significant drop in the catalytic activity or selectivity. Using the pegylated catalyst H-Pro-Pro-Asp-Ahx-NH(CH2CH2O)3CH3, only 0.5 mol % are necessary to obtain aldol products in up to 96% yield and 91% enantiomeric excess. In all cases, enantioselectivities are comparable to those obtained with the parent catalyst H-Pro-Pro-Asp-NH2. Thus, immobilization of H-Pro-Pro-Asp-NH2 on Tentagel as well as pegylation led to catalysts with selectivities comparable to the nonmodified catalyst, exhibiting additional distinct advantages such as facile reusability, ease of handling, higher solubility, and thereby greater versatility. handling, higher solubility, and thereby greater versatility.

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Increased Structural Complexity Leads to Higher Activity: Peptides as Efficient and Versatile Catalysts for Asymmetric Aldol Reactions

Cited by 266 publications

References 15 publications

Organocatalytic Asymmetric Synthesis Using Proline and Related Molecules. Part 1

Organocatalytic Asymmetric Synthesis Using Proline and Related Molecules. Part 1

Organocatalytic Asymmetric Synthesis Using Proline and Related Molecules. Part 2.

Solid‐supported and pegylated H–Pro–Pro–Asp–NHR as catalysts for asymmetric aldol reactions

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