Synthesis of 3‐Carbamoyl β‐Lactams via Manganese(III)‐Promoted Cyclization of N‐Alkenylmalonamides

Punda, Paweł; Ponikiewski, Łukasz; Makowiec, Sławomir

doi:10.1002/hlca.201200646

Cited by 5 publications

(1 citation statement)

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“…The main methods include the [2+2] cycloaddition of acyl ketenes, generated by various methods, with imines [11][12][13][14] and the Wolff rearrangement of γ-amino-α-diazo-β-keto esters followed by intramolecular cyclization. [15,16] Additionally, the manganese(III)-promoted cyclization of N-alkenyl malonamides [17,18] and the Cu(I)-catalyzed reaction of propiolic acid derivatives with nitrones (Kinugasa reaction) [19][20][21] should also be mentioned, as well as intramolecular C-H insertion using diazo monomalonamides under the action of various catalysts which is a very efficient method for preparing β-lactam esters. [22][23][24] Scheme 1.…”

Section: Introductionmentioning

confidence: 99%

Access to 2-Oxoazetidine-3-carboxylic Acids Derivatives via Thermal Microwave-Assisted Wolff Rearrangement of 3-Diazotetramic Acids in the Presence of Nucleophiles

Lyutin,

Krivovicheva,

Kantin

et al. 2024

Preprint

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In this work, we report an efficient approach to 2-oxoazetidine-3-carboxylic acid derivatives based on thermally promoted Wolff rearrangement of diazo tetramic acids in the presence of nucleophiles. The method allows easy variation of the substituent in the exocyclic acyl group by introducing different N-, O- and S-nucleophilic reagents into the reaction. The reaction of chiral diazo tetramic acids leads exclusively to trans-diastereomeric β-lactams. The use of variously substituted diazo tetramic acids, including spirocyclic derivatives, as well as a wide range of nucleophiles provides access to a structural diversity of medically relevant 2-oxoazetidine-3-carboxylic acids amides and esters.

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Section: Introductionmentioning

confidence: 99%

Access to 2-Oxoazetidine-3-carboxylic Acids Derivatives via Thermal Microwave-Assisted Wolff Rearrangement of 3-Diazotetramic Acids in the Presence of Nucleophiles

Lyutin,

Krivovicheva,

Kantin

et al. 2024

Preprint

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Manganese( III ) acetate

Ho¹,

Fieser²,

Fieser³

et al. 2017

Fieser and Fieser's Reagents for Organic Synthesis

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ChemInform Abstract: Synthesis of 3‐Carbamoyl β‐Lactams via Manganese(III)‐Promoted Cyclization of N‐Alkenylmalonamides.

2014

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Manganese(III)-promoted cyclization of N-alkenylmalonamides (¼ N-alkenylpropanediamides) gave 3-(aryl/(alkylamino)carbonyl) b-lactams as well as 3-(aryl/(alkylamino)thiocarbonyl) b-lactams. The relative configuration of the obtained products was unambiguously determined by X-ray crystallography. The proposed method is very useful for the one-pot synthesis of a number of 3-(aryl/ (alkylamino)carbonyl) b-lactams, especially those containing an amino(thiocarbonyl) moiety, which are not selectively accessible by other methods.Introduction. -For the period of almost seven decades, after the first documented use of penicillin had begun, the b-lactam system has been at the center of interest of organic chemistry. Of course, the main stream of research is related to the potential applications of b-lactams as effective antimicrobial chemotherapeutics. However, purely synthetic studies are also known, for example, the Ojima b-Lactam Synthon Method for the preparation of peptides [1], amino acids [2], and hydroxy acids [3].So far, several methods for the preparation of the azetidine-2-one system have been developed, e.g., carbodiimide coupling of b-amino acids [4], condensation with PPh 3 pyridine disulfide developed by Ohno and co-workers [5], Grignard reagent-mediated cyclization of silyl esters of amino acids [6], cyclizations using an epoxide system and anion-stabilizing group [7], intramoleular electrophilic addition to olefins [8], or radical cyclization of 3-oxoenamides [9]. However, it should be noted that the first method used for the preparation of b-lactams via the cycloaddition of ketenes to imines, proposed by Staudinger at the beginning of the 19th century [10], after several modification and improvements, is still one of the most popular methods for the preparation of these compounds.Recently, we have reported a variation of the Staudinger method for the preparation of 3-carbamoyl b-lactams by addition of aldimines to carbamoyl ketenes, generated from 5-[hydroxy(arylamino)methylidene]-2,2-dimethyl-1,3-dioxane-4,6-dione [11]. Despite many advantages, mainly due to the simplicity of this method, we were not able to obtain models of 3-carbamoyl b-lactams with alkyl groups or S in the carbamoyl fragment.As mentioned already, an alternative way of forming b-lactams may be the cyclization of enamides, which was demonstrated by Trogolo and co-workers [9] in the oxidative cyclization of 3-oxo enamides. On the other hand, we have recently developed a method for the preparation of N-alkenylmalonamides (¼ N-alkenylpropanediamides) and N-alkenylthiomalonamides 3 from carbamoyl and thiocarbamoyl Meldrums acids 1, respectively [12].

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Synthesis of 3‐Carbamoyl β‐Lactams via Manganese(III)‐Promoted Cyclization of N‐Alkenylmalonamides

Cited by 5 publications

References 29 publications

Access to 2-Oxoazetidine-3-carboxylic Acids Derivatives via Thermal Microwave-Assisted Wolff Rearrangement of 3-Diazotetramic Acids in the Presence of Nucleophiles

Access to 2-Oxoazetidine-3-carboxylic Acids Derivatives via Thermal Microwave-Assisted Wolff Rearrangement of 3-Diazotetramic Acids in the Presence of Nucleophiles

Manganese( III ) acetate

ChemInform Abstract: Synthesis of 3‐Carbamoyl β‐Lactams via Manganese(III)‐Promoted Cyclization of N‐Alkenylmalonamides.

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