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Special Issue "Advances in Spiro Compounds"

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organic Synthesis".

Deadline for manuscript submissions: 30 April 2018

Special Issue Editors

Guest Editor
Prof. Dr. László Somsák

Department of Organic Chemistry, University of Debrecen, P.O. Box 400, Debrecen H-4002, Hungary
Website | E-Mail
Interests: C-glycosyl compounds; glycals; exo-glycals; sugar derived spirocycles; radical and carbene mediated transformations of carbohydrates; glycosidase and glycogen phosphorylase inhibitors; glycomimetics and glycopeptidomimetics; antidiabetics
Guest Editor
Prof. Dr. Anthony J. Burke

Department of Chemistry and Centro de Química de Évora, Institute for Research and Advanced Training and School of Science and Technology, University of Évora Colégio Luís Verney, Rua Romão Ramalho, 59, 7000 Évora, Portugal
Website | E-Mail
Interests: medicinal chemistry; drug design; organic synthesis; catalysis; organocatalysis; transition-metal mediated reactions; small molecule synthesis; mechanism elucidation; polymer synthesis; NMR

Special Issue Information

Dear Colleagues,

Spiro compounds (also named as spiranes following the suggestion of Adolf von Baeyer as early as 1900) are ubiquitous molecules, which contain a fused bicyclic system that share a single atom. A search for the key term “spiro” in the SciFinder database at the beginning of April 2017 resulted in more than 147,000 hits including 5000–6000 publications per annum after 2010. This enormous research activity encompasses a large number of fields in chemistry (especially organic and medicinal chemistry—with an emphasis on heterocyclic systems), but also includes pharmacology, crystallography, materials science, physics, biochemistry, molecular biology, engineering, energy and fuels, just to mention the most active areas. The immense interest in spirocycles, besides their unique features related to isolation from natural sources, synthesis and stereochemistry, is fuelled by an extremely wide range of useful properties, that comprise among others anti-cancer, antibacterial, antifungal, anti-diabetic, anti-HIV, cytotoxic, diuretic, spasmolytic, antiphlogistic, anti-hypertensive, anti-depressant, anxiolytic, anti-fouling, anti-feedant, herbicidal, plant growth regulatory effects; photochromism; and hole-transporting ability.

These properties have been translated into several practical applications which include marketed drugs; ophtalmic lenses and sunscreening (for instance in sunglasses); auxiliary compounds in stereoselective syntheses; electronic displays and optical data storage devices, etc. In addition, many other utilizations, such as new medications, chemical biosensing, controlled release drug delivery, molecular switches, and solar cells, are in a developmental phase.

With regard to pharmaceutical applications, it should also be mentioned that at the current time, driven by the ever-increasing pace of drug discovery, medicinal chemists are turning to new unexplored regions of chemical space in the quest to find more potent medicines. Thus, unusual strained spirocyclic bioisosteres are important targets, as they show diverse new biological activities. Moreover, besides potentially modulating binding potency and specificity, spirocyclic scaffolds may also improve bioavailability and metabolic stability, key issues when developing new pharmacological entities.

This forthcoming Special Issue of Molecules entitled “Advances in Spiro Compounds“ will be devoted to this amazing class of compounds, covering recent key findings in any of the above research fields.

Prof. Dr. László Somsák
Prof. Dr. Anthony J. Burke
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1800 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • spiro compounds
  • isolation
  • molecular design
  • synthesis
  • medicinal chemistry
  • biological activity
  • drugs
  • inhibition
  • conformational restriction
  • photochromism
  • polymers
  • applications

Published Papers (7 papers)

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Research

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Open AccessArticle Organocatalytic Access to Enantioenriched Spirooxindole-Based 4-Methyleneazetidines
Molecules 2017, 22(11), 2016; doi:10.3390/molecules22112016 (registering DOI)
Received: 30 October 2017 / Revised: 15 November 2017 / Accepted: 17 November 2017 / Published: 21 November 2017
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Abstract
This work describes the synthesis of enantioenriched spiro compounds, incorporating the azetidine and the oxindole motifs. The preparation relies on a formal [2 + 2] annulation reaction of isatin-derived N-tert-butylsulfonyl ketimines with allenoates. The asymmetric induction is secured by an
[...] Read more.
This work describes the synthesis of enantioenriched spiro compounds, incorporating the azetidine and the oxindole motifs. The preparation relies on a formal [2 + 2] annulation reaction of isatin-derived N-tert-butylsulfonyl ketimines with allenoates. The asymmetric induction is secured by an organocatalytic strategy, exploiting a bifunctional cinchona-type β-isocupridine-based catalyst. Some post-transformation products, including unexpected spiropyrroline and 3,3-disubstituted oxindole derivatives, are also presented. Full article
(This article belongs to the Special Issue Advances in Spiro Compounds)
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Open AccessArticle 9,10-Dihydrophenanthrene with Two Spiro(dibenzocycloheptatriene) Units: A Highly Strained Caged Hydrocarbon Exhibiting Reversible Electrochromic Behavior
Molecules 2017, 22(11), 1900; doi:10.3390/molecules22111900
Received: 19 October 2017 / Revised: 3 November 2017 / Accepted: 3 November 2017 / Published: 4 November 2017
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Abstract
The title dispiro hydrocarbon 1 was designed as a new electrochromic material. This multiply clamped hexaphenylethane-type electron donor was prepared from 2,2’-diiodobiphenyl via biphenyl-2,2’-diylbis(dibenzotropylium) 22+ salt. X-ray analysis of 1 revealed a highly strained structure as reflected by an elongated “ethane” bond
[...] Read more.
The title dispiro hydrocarbon 1 was designed as a new electrochromic material. This multiply clamped hexaphenylethane-type electron donor was prepared from 2,2’-diiodobiphenyl via biphenyl-2,2’-diylbis(dibenzotropylium) 22+ salt. X-ray analysis of 1 revealed a highly strained structure as reflected by an elongated “ethane” bond [bond length: 1.6665(17) Å] and nearly eclipsed conformation. The weakened bond was cleaved upon two-electron oxidation to regenerate the deeply colored dication 22+. The reversible interconversion between 1 and 22+ is accompanied not only by a drastic color change but also by C–C bond formation/cleavage. Thus, the voltammogram showed a pair of well-separated redox waves, which is characteristic of “dynamic redox (dyrex)” behavior. The tetrahydro derivative of 1 with two units of spiro(dibenzocycloheptadiene), which suffers from more severe steric congestion, was also prepared. The crystallographically determined bond length for the central C–C bond [1.705(4) Å] is greatest among the values reported for 9,9,10,10-tetraaryl-9,10-dihydrophenanthrene derivatives. Full article
(This article belongs to the Special Issue Advances in Spiro Compounds)
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Open AccessFeature PaperArticle Fluorescent “Turn-Off” Detection of Fluoride and Cyanide Ions Using Zwitterionic Spirocyclic Meisenheimer Compounds
Molecules 2017, 22(11), 1842; doi:10.3390/molecules22111842
Received: 27 September 2017 / Revised: 25 October 2017 / Accepted: 26 October 2017 / Published: 27 October 2017
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Abstract
Stable zwitterionic spirocyclic Meisenheimer compounds were synthesized using a one-step reaction between picric acid and diisopropyl (ZW1) or dicyclohexyl (ZW3) carbodiimide. A solution of these compounds displays intense orange fluorescence upon UV or visible light excitation, which can be quenched or “turned-off” by
[...] Read more.
Stable zwitterionic spirocyclic Meisenheimer compounds were synthesized using a one-step reaction between picric acid and diisopropyl (ZW1) or dicyclohexyl (ZW3) carbodiimide. A solution of these compounds displays intense orange fluorescence upon UV or visible light excitation, which can be quenched or “turned-off” by adding a mole equivalent amount of F or CN ions in acetonitrile. Fluorescence is not quenched in the presence of other ions such as Cl, Br, I, NO2, NO3, or H2PO4. These compounds can therefore be utilized as practical colorimetric and fluorescent probes for monitoring the presence of F or CN anions. Full article
(This article belongs to the Special Issue Advances in Spiro Compounds)
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Figure 1

Open AccessFeature PaperArticle Glucopyranosylidene-Spiro-Thiazolinones: Synthetic Studies and Determination of Absolute Configuration by TDDFT-ECD Calculations
Molecules 2017, 22(10), 1760; doi:10.3390/molecules22101760
Received: 25 September 2017 / Revised: 18 October 2017 / Accepted: 18 October 2017 / Published: 19 October 2017
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Abstract
Reactions of O-peracylated C-(1-bromo-β-d-glucopyranosyl)formamides with thioamides furnished the corresponding glucopyranosylidene-spiro-thiazolin-4-one. While O-debenzoylations under a variety of conditions resulted in decomposition, during O-deacetylations the addition of MeOH to the thiazolinone moiety was observed, and with EtOH and water
[...] Read more.
Reactions of O-peracylated C-(1-bromo-β-d-glucopyranosyl)formamides with thioamides furnished the corresponding glucopyranosylidene-spiro-thiazolin-4-one. While O-debenzoylations under a variety of conditions resulted in decomposition, during O-deacetylations the addition of MeOH to the thiazolinone moiety was observed, and with EtOH and water similar adducts were isolated or detected. The structure and stereochemistry of the new compounds were established by means of NMR and electronic circular dichroism (ECD) data supported by time-dependent density functional theory ECD (TDDFT-ECD) calculations. TDDFT-ECD calculations could efficiently distinguish the proposed epimeric products having different absolute configuration in the spiro heterocyclic ring. Full article
(This article belongs to the Special Issue Advances in Spiro Compounds)
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Open AccessArticle Spiropyran-Isoquinoline Dyad as a Dual Chemosensor for Co(II) and In(III) Detection
Molecules 2017, 22(9), 1569; doi:10.3390/molecules22091569
Received: 4 August 2017 / Accepted: 10 September 2017 / Published: 19 September 2017
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Abstract
Spiropyran derivatives have been studied as light-regulated chemosensors for a variety of metal cations and anions, but there is little research on chemosensors that simultaneously detect multiple metal cations. In this study, a spiropyran derivative with isoquinoline, SP-IQ, was prepared and it
[...] Read more.
Spiropyran derivatives have been studied as light-regulated chemosensors for a variety of metal cations and anions, but there is little research on chemosensors that simultaneously detect multiple metal cations. In this study, a spiropyran derivative with isoquinoline, SP-IQ, was prepared and it functions investigated as a light-regulated sensor for both Co2+ and In3+ cations. A colorless nonfluorescent SP-IQ converts to a pink-colored fluorescent MC-IQ by UV irradiation or standing in the dark, and MC-IQ returns to SP-IQ with visible light. Upon UV irradiation with the Co2+ cation for 7 min, the stronger absorption at 540 nm and the similar fluorescence intensity at 640 nm are observed, compared to when no metal cation is added, due to the formation of a Co2+ complex with pink color and pink fluorescence. When placed in the dark with the In3+ cation for 7 h, the colorless solution of SP-IQ changes to the In3+ complex with yellow color and pink fluorescence, which shows strong absorption at 410 nm and strong fluorescence at 640 nm. Selective detection of the Co2+ cation with UV irradiation and the In3+ cation in the dark could be possible with SP-IQ by both absorption and fluorescence spectroscopy or by the naked eye. Full article
(This article belongs to the Special Issue Advances in Spiro Compounds)
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Open AccessArticle An Efficient Synthesis of Spiro[indoline-3,9′-xanthene]trione Derivatives Catalyzed by Magnesium Perchlorate
Molecules 2017, 22(8), 1295; doi:10.3390/molecules22081295
Received: 19 July 2017 / Revised: 31 July 2017 / Accepted: 1 August 2017 / Published: 4 August 2017
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Abstract
A simple and efficient method for the synthesis of spiro[indoline-3,9′-xanthene]trione derivatives by means of condensation between isatins and 1,3-cyclohexanedione in the presence of a catalytic amount of magnesium perchlorate at 80 °C in 50% aqueous ethanol medium has been described. Notably, the present
[...] Read more.
A simple and efficient method for the synthesis of spiro[indoline-3,9′-xanthene]trione derivatives by means of condensation between isatins and 1,3-cyclohexanedione in the presence of a catalytic amount of magnesium perchlorate at 80 °C in 50% aqueous ethanol medium has been described. Notably, the present method offers desirable advantages of good yields, simplicity of workup procedure, easy purification, and reduced reaction times. Full article
(This article belongs to the Special Issue Advances in Spiro Compounds)
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Review

Jump to: Research

Open AccessReview Recent Advances in the Synthesis of Spiroheterocycles via N-Heterocyclic Carbene Organocatalysis
Molecules 2017, 22(11), 1882; doi:10.3390/molecules22111882
Received: 26 September 2017 / Accepted: 30 October 2017 / Published: 8 November 2017
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Abstract
Spiroheterocycles are regarded as a privileged framework because of their wide distribution in various natural products and synthetic molecules and promising bioactivities. This review focuses on the recent advances in the synthesis of spiroheterocycles by using the strategy of N-heterocyclic carbene (NHC)
[...] Read more.
Spiroheterocycles are regarded as a privileged framework because of their wide distribution in various natural products and synthetic molecules and promising bioactivities. This review focuses on the recent advances in the synthesis of spiroheterocycles by using the strategy of N-heterocyclic carbene (NHC) organocatalysis, and is organized based on the stereoselectivity and the reactive intermediates. According to the stereochemistry, this review was divided into two main parts, covering racemic and enantioselective versions. In each part, we firstly describe the synthetic transformations using nucleophilic Breslow intermediates, and then discuss the reactions that employ electrophilic acylazolium or radical cation intermediates. With those distinct catalytic activation modes of NHC organocatlysis, we expect this synthetic protocol will possibly produce new molecules with structural novelty and complexity, which may warrant further research in the field of drug discovery. Full article
(This article belongs to the Special Issue Advances in Spiro Compounds)
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Figure 1

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