Synthetic macrocyclic di- and tetraester compounds

Bradshaw, Jerald S.; Maas, G.; Izatt, Reed M.; Christensen, James J.

doi:10.1021/cr60317a004

Cited by 99 publications

(29 citation statements)

References 12 publications

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“…[4] Since the seminal discovery of the crown ethers by Pedersen, [5] a plethora of nonnatural macrocycles, mimicking the properties of the natural ionophores, have been prepared by a variety of synthetic approaches. A first comprehensive review covering the synthesis and the cation-binding properties of synthetic ionophores, including macrocyclic di-and tetralactones, was published by Bradshaw et al in 1979. [6] The synthesis of the first macrocyclic bislactone, compound 1 (Scheme 1), incorporating a malonate ester moiety, dihedral angles: all ester moieties adopt anti conformations whereas the planes of the carboxy moieties of each malonate residue arrange in an approximately orthogonal fashion.…”

Section: Introductionmentioning

confidence: 99%

“…A first comprehensive review covering the synthesis and the cation-binding properties of synthetic ionophores, including macrocyclic di-and tetralactones, was published by Bradshaw et al in 1979. [6] The synthesis of the first macrocyclic bislactone, compound 1 (Scheme 1), incorporating a malonate ester moiety, dihedral angles: all ester moieties adopt anti conformations whereas the planes of the carboxy moieties of each malonate residue arrange in an approximately orthogonal fashion. The latter geometry is enforced by the macrocyclic structures, as revealed by a conformational search in the Cambridge Structural Database.…”

Section: Introductionmentioning

confidence: 99%

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Macrocyclic Cyclo[n]malonates – Synthetic Aspects and Observation of Columnar Arrangements by X‐ray Crystallography

Chronakis¹,

Brandmüller²,

Kovacs³

et al. 2006

Eur J Org Chem

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A variety of achiral and chiral macrocyclic oligomalonates were synthesised in a one-step procedure through condensation of malonyl dichloride with α,ω-diols. We have investigated the applicability of this method by varying the length and type of the spacers in the diol. Product distribution analysis revealed that the preferential formation of monomeric, dimeric, or trimeric macrocyclic malonates can be controlled by choosing diols with specific spacers connecting the hydroxy groups. Of special interest are the macrocyclic bismalonates, as they show pronounced crystallisability and arrange into columnar motifs in the solid state. They feature distinctive

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Macrocyclic Cyclo[n]malonates – Synthetic Aspects and Observation of Columnar Arrangements by X‐ray Crystallography

Chronakis¹,

Brandmüller²,

Kovacs³

et al. 2006

Eur J Org Chem

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“…7 Besides coordinative bonds that permit formation of compounds with a structural diversity, depending on the coordination geometry of the metallic ion, 8 other intermolecular interactions such as hydrogen bonds, C-HÁÁÁ or -interactions, van der Waals, and so on, [9][10][11] offer premises for the organization of individual molecules into well-defined supramolecular assemblies. [12][13][14][15][16][17] In recent years, noncovalent interactions and self-assembly phenomenon have attracted attention due to their use in sensors, photonic devices and catalysts, as well as in host-guest chemistry. 18,19 The first step in achieving the desired supramolecular metal containing structure consists in choosing an appropriate ligand.…”

Section: Introductionmentioning

confidence: 99%

Coordination polymer of copper with a silicon-containing Schiff base

Zaltariov¹,

Cazacu²,

Vlad³

et al. 2015

High Performance Polymers

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A Schiff base was prepared by condensation reaction of 2,6-diformyl-4-methylphenol with trimethylsilyl-methyl-p-aminobenzoate and it was further used, without isolation, as a ligand for copper (Cu(II)) ions. The structure of the resulting coordination complex was evidenced by spectral techniques (Fourier transform infrared spectroscopy, nuclear magnetic resonance and ultraviolet-visible spectroscopy) and by single crystal X-ray diffraction, which revealed a covalent onedimensional (1D) structure where neutral molecular units (Cu(II) coordination polymer [CuL 2 ]) are linked through the bridging oxygen atoms. The 1D polymeric chains are associated by intermolecular C-HÁÁÁO hydrogen bonding to form two-dimensional supramolecular layers. The polymeric nature of the compound was also supported by the presence of glass transition in differential scanning calorimetry trace. This coordination polymer forms spherical aggregates in a nonpolar medium (hexane) as was emphasized by transmission electron microscopy image taken on the film remained after solvent evaporation. The thermogravimetrical analysis indicates a good stability for the Cu(II) coordination polymer and the biological tests revealed good antibacterial and antifungal activities.

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“…As shown by X-ray crystallography, CALB, compared to other lipases, has very limited space available at the active site pocket, which is composed of two channels, one hosting the acyl part and the other hosting the alcohol moiety of the substrate. 17 The acyl channel is more spacious than the alcohol channel, and therefore the enzyme is expected to exert a broad specificity towards acyl Scheme 2 C. antarctica-catalyzed reaction of diols 1a-f with succinic anhydride (2) donors and a much higher degree of selectivity towards alcohol substrates. 18 These considerations are in line with our observations.…”

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confidence: 99%

Synthesis of Macrocyclic Dilactones through Lipases

Bosch¹,

Guerrero²

2005

Synlett

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We report herein a selective and efficient method to prepare macrocyclic dilactones in good yields from diols and succinic anhydride through a biocatalytic condensation reaction.The synthetically challenging structures of macrolides have attracted the attention of organic chemists for a long time but only recently have efforts in this direction begun to gain momentum. 1 Particularly attractive are macrocyclic dilactones, not only because of their remarkable biological activities but also because of their ability to complex and transport alkali metal cations and their utilization in the perfume industry. 2 However, only a limited number of methods for preparation of macrocyclic dilactones are currently available. They comprise the reaction of the dicesium salts of pyridindicarboxylic acids with dibromides, 3 reaction of dioxodioic acid chlorides with oligoethylene glycols, 4 condensation of the dipotassium salt of maleic, citraconic and o-phthalic acids with alkyl or alkynyl dibromides, 5 condensation of benzyl bromides with homologous series of dicarboxylic acids, 6 reaction of substituted dicarboxylic acid chlorides with w-bromoalcohols followed by reaction with lithium or potassium salts of dicarboxyxlic acids, 7 condensation of diacid chlorides with diols using metal carbonates and KF as bases under phase-transfer catalysis, 8 or via cyclization of (wcarboxyalkyl)diphenylsulfonium salts in the presence of cesium carbonate under high dilution conditions. 9 However, many of these methods provide mixtures of dilactones and tetralactones, in some cases in low yields and under harsh reaction conditions. Only one case has been found in the literature in which macrocyclic lactones are prepared enzymatically by reaction of acyclic diacids with diols in the presence of C. cylindracea, Pseudomonas sp. and porcine pancreatic lipase. 10 However, even in this case mixtures of mono-and dilactones were obtained in moderate yields, the dilactones being produced in the range of 5-19% yield.In this paper we present a simple and high yielding method to selectively prepare macrocyclic dilactones by reaction of 1,n-diols with succinic anhydride 11 in the presence of Candida Antarctica B lipase (CALB, Novozyme 435). Intramolecular lactonization of long chain hydroxyesters with lipase P (Pseudomonas sp.) to provide pheromone components of grain beetles 12 or a key intermediate for the synthesis of the anti-obesity agent tetrahydrolipstatin with PPL has been described. 13 Initially, we tested the reaction of 1,6-hexanediol and succinic anhydride in the presence of several lipases (PS, AP-6, Mucor miehei, Candida rugosa, CALB and Pseudomonas fluorescens) in a number of solvents and under different experimental conditions. Scheme 1 Enzymatic reaction of diol 1d with succinic anhydride 2The reaction resulted in a mixture of variable amounts of starting diol 1d, hydroxyacid 3d, dilactone 4d and diacid 5d 14 (Scheme 1) by GC analysis after esterification with MeI/K 2 CO 3 . 15 Under these conditions, compounds 3d and 5d are converted into...

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Synthetic macrocyclic di- and tetraester compounds

Cited by 99 publications

References 12 publications

Macrocyclic Cyclo[n]malonates – Synthetic Aspects and Observation of Columnar Arrangements by X‐ray Crystallography

Macrocyclic Cyclo[n]malonates – Synthetic Aspects and Observation of Columnar Arrangements by X‐ray Crystallography

Coordination polymer of copper with a silicon-containing Schiff base

Synthesis of Macrocyclic Dilactones through Lipases

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