Eine einfache Herstellung von ω-Alkoxylactamen durch anodische Alkoxylierung

Mitzlaff, M.; Warning, Klaus; Rehling, H.

doi:10.1055/s-1980-29008

Cited by 23 publications

(5 citation statements)

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“…So far, the most important methods are based on electrochemical alkoxylation ( Scheme 1 /I), which is very efficient (especially for electrochemical decarboxylative α-alkoxylation of α-amino acid derivatives 5 ) but requires additional, sometimes expensive equipment and basic knowledge of electrochemistry. 23 − 35 Therefore, synthetic chemists are often reluctant to employ such strategies. There are several other interesting methods for the synthesis of N -protected 1-aminoalkylphosphonium salts described in the literature.…”

Section: Introductionmentioning

confidence: 99%

“…The most significant challenges regarding the use of phosphonium salts on a large scale involve difficulties with their preparation. So far, the most important methods are based on electrochemical alkoxylation (Scheme /I), which is very efficient (especially for electrochemical decarboxylative α-alkoxylation of α-amino acid derivatives 5 ) but requires additional, sometimes expensive equipment and basic knowledge of electrochemistry. − Therefore, synthetic chemists are often reluctant to employ such strategies. There are several other interesting methods for the synthesis of N -protected 1-aminoalkylphosphonium salts described in the literature. − However, in most cases, they are multistep, time- and labor-consuming, and have a narrow scope of application, which in practice is limited to N -acylaminomethylphosphonium salts (see also Table S1, Supporting Information) …”

Section: Introductionmentioning

confidence: 99%

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Synthesis of N-Protected 1-Aminoalkylphosphonium Salts from Amides, Carbamates, Lactams, or Imides

2021

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This report describes the development and optimization of the one-pot method for the synthesis of N -protected 1-aminoalkylphosphonium salts based on the three-component coupling of aldehydes and either amides, carbamates, lactams, imides, or urea in the presence of triarylphosphonium salts. The proposed strategy is very efficient and easy to carry out even on a larger scale (20 g) in any typical laboratory. Most reactions occur at temperatures between 50 and 100 °C in a short time (1–2 h) without requiring any catalyst, and simple workup procedures afford good to excellent yields. The exceptions are condensations with imides, which require much higher temperatures (150–170 °C) and longer reaction times (even 30 h). The possibility of carrying out the synthesis under solvent-free conditions (neat reactions) is also demonstrated. It is especially important for less reactive substrates (imides), and reactions required high temperature (or generally harsher conditions). Finally, we prove the developed one-pot methodology can be successfully applied for the synthesis of structurally diverse N -protected 1-aminoalkylphosphonium salts. Mechanistic studies showed the intermediate products of described couplings are 1-hydroxyalkylphosphonium salts, not N -hydroxyalkylamides, -imides, etc., as initially expected.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Synthesis of N-Protected 1-Aminoalkylphosphonium Salts from Amides, Carbamates, Lactams, or Imides

2021

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“…To the best of our knowledge, the anodic oxidation of α-lactams has never been reported. Like other amides, lactams could also be anodically alkoxylated (or hydroxylated) at the alphaposition to 'N' [30][31][32][33] as shown in Scheme 17.…”

Section: Lactamsmentioning

confidence: 99%

Anodic Oxidation of Aliphatic and Aromatic Amides, Bisamides and Related Derivatives

Becker

2024

ChemElectroChem

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The current comprehensive review covers four main parts, of which some are presented in the form of a personal account. 1. Anodic oxidation of a) N‐alkyl and N,N‐diallyl carbonyl moieties, b) Azacycloalkyl amides and the effect of ring‐size on the outcome, c) Lactams, d) Sulfonamides, and e) The effect of a substituent R attached to carbonyl (N−CO−R) or sulfonamides (N−SO2R) on their oxidation potentials. 2. Anodic oxidation of aromatic amides, in particular of type Ph2CHCONHAr, lacking hydrogen(s) at the α‐position to nitrogen. They undergo three types of bond‐cleavage, yielding a variety of fragmentation products. 3. a) Anodic oxidation of symmetrical bisamides of type ZCONH(CH2)nNHCOZ (Z=Me, Ph, Ar; n=2–4) under constant current electrolysis, in methanol. For n=3, 4 they afford mostly mono‐ and dimethoxylation products. For n=2 they undergo ′CH2−CH2′ bond cleavage to yield fragmentation products. b) Anodic oxidation of symmetrical bisamides of type ArCONH(CH2)2NHCOAr under controlled potential electrolysis, in acetonitrile, leads to gem‐unsymmetrical bisamides of type ArCONHCH2NHCOMe as the major product, in fair yields. 4. Utilization of the anodic process in organic synthesis to form C−C bonds by both intra‐ and inetrmolecular processes; as well as C−O and C−N bonds for generating heterocycles.

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“…149-150 "C (Found: C, 81.9; H, 7.8; N, 4.9. C,9H21N0 requires C, 81.7; H, 7.6; N, 5.0%); m/z 280 ( M + + 1, l%), 236 (9), 222 (12), 180 (loo), and 166 (47); vmax.…”

Section: L-t-butyl-33-diphenylazetidin-2-one (%)mentioning

confidence: 99%

Acyloxylation at the 4-position of azetidin-2-ones

Easton¹,

Love²,

Wang³

1990

J. Chem. Soc., Perkin Trans. 1

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The copper-catalysed reaction of azetidin-2-ones with t-butyl perbenzoate or peracetate affords the corresponding 4-benzoyloxy-and acetoxy-substituted p-lactams, respectively. N -Unsubstituted 4acyloxyazetidinones can be synthesized by dearylation of the N-(4-methoxyphenyl) -substituted products with ceric ammonium nitrate. Acyloxylation of p-lactams that are monosubstituted at C-3 affords predominantly trans-products.4-Acetoxy-and benzoyloxy-substituted azetidin-2-ones have been used extensively in organic synthesis, particularly as precursors of p-lactam antibiotics.Consequently, there is considerable interest in the development of methods for the synthesis of compounds of this type. Here7 we describe a method for the synthesis of 4-acyloxy-substituted azetidinones through the copper-catalysed reaction of p-lactams with t-butyl peresters.The only alternative procedure that has been reported for the direct acyloxylation of p-lactams at the 4-position involves the electrochemical oxidation of azetidin-2-ones in acetic acidacetonitrile.* This latter method is an extension of previous work on the introduction of alkoxy substituents through electrolysis of P-lactam~.~*'~ It has also been reported that oxidation of N-hydroxyazetidines with lead tetra-acetate gives the corresponding 1,4-diacetoxyazetidinones, but this process is thought to occur by 1,4-addition of the oxidizing agent to intermediate nitrones, not by direct substitution of p-lactams.'

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Eine einfache Herstellung von ω-Alkoxylactamen durch anodische Alkoxylierung

Cited by 23 publications

References 0 publications

Synthesis of N-Protected 1-Aminoalkylphosphonium Salts from Amides, Carbamates, Lactams, or Imides

Synthesis of N-Protected 1-Aminoalkylphosphonium Salts from Amides, Carbamates, Lactams, or Imides

Anodic Oxidation of Aliphatic and Aromatic Amides, Bisamides and Related Derivatives

Acyloxylation at the 4-position of azetidin-2-ones

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