Investigation of 1-bromo-3-buten-2-one as building block in organic synthesis

Westerlund, Andreas; Gras, Jean‐Louis; Carlson, Rolf

doi:10.1016/s0040-4020(01)00526-9

Cited by 19 publications

(9 citation statements)

References 14 publications

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“…By NMR spectroscopy they observed that the nucleophilic displacement of bromine seems to take place in the first step, resulting in pyrrolidinone formation. [20] Primary amino compounds have been found to participate in similar reactions to yield nitrogen-containing heterocycles. [21] In the synthesis of simple five-and six-membered nitrogen and sulfur heterocycles, Bunce established, by GC monitoring, higher reactivity of benzylamine with halide than with crotonate and isolated isothiouronium salts, demonstrating that halide displacement is the initial step of the sequence in the sulfur heterocyclisation.…”

Section: Resultsmentioning

confidence: 99%

A New Approach to the Synthesis of N‐Alkylated 2‐Substituted Azetidin‐3‐ones

2006

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We report a one-pot methodology for the synthesis of N-alkylated 2-substituted azetidin-3-ones based on a tandem nucleophilic substitution followed by intramolecular Michael reaction of primary amines with alkyl 5-bromo-4-oxopent-2-enoates, obtained in turn in three steps from levulinic acid. IntroductionSince the azetidin-3-one core has been used as a precursor for the synthesis of the natural sphingosine-type alkaloids penaresidines A and B and penazetidin A, [1] or as an intermediate in the synthesis of polyoxin antibiotics, [2,3] a number of different methodologies to obtain these fourmembered heterocycles have previously been described. [4] Cyclisation based on rhodium carbenoid intramolecular NH insertion has been developed by Seebach for the preparation of some azetidine-containing amino alcohol and amino acid derivatives [5] and by Vederas et al. for the synthesis of keto-glutamine analogues, [6] while De Kimpe has recently reported the synthesis of 4-alkyl-1-benzhydryl-2-(methoxymethyl)azetidin-3-ol as the result of stereoselective alkylation at the C-4 position of the corresponding azetidin-3-one obtained through a high-temperature reaction of an N-(diphenylmethylidene)-3-bromoamine precursor. [7] Azetidin-3-ones could also be obtained from the corresponding azetidin-3-ol precursors by use of pyridinium dichromate or Swern-type oxidation conditions. [8] As part of a recently started program aiming at the transformation of non-food/non-feed agricultural products, byproducts and waste materials into commodity chemicals we were interested in fine chemistry application of polyfunctionalised building blocks. One such derivative is 4-oxopentanoic acid or levulinic acid (LA; 1), traditionally obtained through the controlled degradation of hexose sugars by mineral acids.[9] The increasing number of patents directed towards the production of levulinic acid demonstrates its potential as an important basic chemical that could now be cost-efficiently produced from raw materials such as wood, [a] 2440A mechanistic interpretation of these reactions and an attempted enantioselective approach are also described. Germany, 2006) starch, cellulose-containing waste materials, recycled paper, or agricultural residues.[10]Beside its conversion into methyltetrahydrofuran, a fuel extender, or into δ-aminolevulinic acid, a biodegradable broad spectrum herbicide, [11] levulinic acid (1) also offers a great number of other synthetic transformations, [12] such as the synthesis of fused heterocycles prepared from norbornane amino acids and diamines [13] or the synthesis of the antibiotic lissoclinolide. [14] For a recent synthetic endeavour we needed ethyl 5-bromo-4-oxopent-2-enoate (3a) as key intermediate. This levulinic acid derivative appeared to be an even more versatile intermediate for further transformations such as Diels-Alder reactions, coupling reactions, nucleophilic substitutions and conjugate additions, and it was speculated that nucleophilic substitution combined with intramolecular Michael reaction should ope...

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Section: Resultsmentioning

confidence: 99%

A New Approach to the Synthesis of N‐Alkylated 2‐Substituted Azetidin‐3‐ones

2006

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“…Spectroscopic data were in agreement with literature values. [9] 2-Benzyl-1-phenylpentane-2,4-diol, compound S11…”

Section: Ohmentioning

confidence: 99%

“…An initial screen of TM fluorides and alcohol activating groups revealed CuF2 and DIC-derived O-alkylisourea as a promising system for the deoxyfluorination of benchmark substrate 1a (Table 1; see SI for full details). Optimization delivered a system where Cu(I)-catalyzed formation of O-alkylisourea 9 followed by deoxyfluorination using CuF2 at 100 ºC gave 2a in 78% isolated yield and with clean SN2 (entry 1). [10][11][12] Several optimization points are worth noting (for full optimization, see Supporting Information): (1) The reaction required formation of the O-alkylisourea prior to addition of CuF2.…”

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confidence: 99%

Deoxyfluorination Using CuF2

Sood¹,

Champion²,

Dawson³

et al. 2019

Preprint

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<div>Deoxyfluorination is a primary method for the formation of C–F bonds. Bespoke reagents are commonly used due to issues associated with the low reactivity of metal fluorides. Here, we report the development of a simple strategy for deoxyfluorination using first-row transition metal fluorides that overcomes these limitations. Using CuF2 as an exemplar, activation of an O-alkylisourea adduct formed in situ allows effective nucleophilic fluoride transfer to a range of primary and secondary alcohols. Spectroscopic investigations have been used to probe the origin of the enhanced reactivity of CuF2. The utility of the process towards enabling 18F-radiolabeling is also presented.</div>

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“…1-Bromobut-3-en-2-one reacted with a primary amine in the presence of potassium carbonate to afford 3pyrrolidines 42 (R = Bn; t-Bu) through an intramolecular Michael reaction (Scheme16) [18]. …”

Section: Scheme 14mentioning

confidence: 99%

“…Reduction of 3-pyrrolidinones with lithium aluminium hydride or sodium bohydride afforded 3-pyrrolidinols 123 (R = alkyl; cycloalkyl and aryl) (Scheme 48) [18,39,55,56]. Diethyl 4-oxopyrrolidine-1,3-dicarboxylate was reduced over PtO 2 or Raney nickel as a catalyst to diethyl 4hydroxypyrrolidine-1,3-dicarboxylate 124 (Figure 3) [36].…”

Section: Reduction To 3-pyrrolidinolsmentioning

confidence: 99%

Synthesis and reactions of 3‐pyrrolidinones

Amer

Hammouda

Abdel‐Wahab

et al. 2008

Journal of Heterocyclic Chem

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N O R R 1 I This review presents a survey of the synthetic methods and reactions of 3-pyrrolidinones I (R = H, alkyl, acyl, ester; R 1 = H, alkyl, cyano, ester, etc). 3-Pyrrolidinones are synthetically versatiles substrate, as they can be used for synthesis of a large variety of heterocyclic compounds, such as indoles and 5-deazapteroic acid analogues and as a raw material for drug synthesis. The high reactivity of an active methylene group next to the carbonyl of the pyrrolidine ring is useful for various syntheses.

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Investigation of 1-bromo-3-buten-2-one as building block in organic synthesis

Cited by 19 publications

References 14 publications

A New Approach to the Synthesis of N‐Alkylated 2‐Substituted Azetidin‐3‐ones

A New Approach to the Synthesis of N‐Alkylated 2‐Substituted Azetidin‐3‐ones

Deoxyfluorination Using CuF2

Synthesis and reactions of 3‐pyrrolidinones

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