From (Phenylsulfanyl)cycloalkanecarbaldehydes to Optically Active Spirocyclic Tetrahydrofurans: Stereospecific Resolution of Symmetric Aldehydes through (<i>S</i>)‐Proline‐Catalysed Aldol Reaction

Secci, Francesco; Frongia, Angelo; Rubanu, Maria Grazia; Sechi, Maria Laura; Sarais, Giorgia; Arca, Massimiliano; Piras, Pier Paolo

doi:10.1002/ejoc.201402653

Cited by 14 publications

(3 citation statements)

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“…This notwithstanding, in the peculiar case of qsal-X – (qsal-X – = monosubstituted quinolylsalicylaldiminate; X = H, OMe, F, Cl, Br, I) Fe III tris-complexes, the B3LYP* functional was recently proven to overestimate the HS–LS enthalpy difference Δ H SCO . In this work, based on the very good results achieved in the past on a variety of both organic − and inorganic systems, − we turned to test the hybrid functional mPW1PW by Adamo and Barone, paralleled by the Def2SVP all-electron split-valence BS, including polarization functions …”

Section: Resultsmentioning

confidence: 99%

Structural Diversity in a New Series of Halogenated Quinolyl Salicylaldimides-Based Fe^III Complexes Showing Solid-State Halogen-Bonding/Halogen···Halogen Interactions

Sahadevan

Cadoni

Monni

et al. 2018

Crystal Growth & Design

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A new series of tridentate N-8-quinolyl-salicylaldimine ligands, Hqsal-5,7-X 2 [X = Cl(1), Br(2), I(3)], halosubstituted at the 5,7 position of the aminoquinoline moiety and their corresponding complexes with Fe III were synthesized and formulated as [Fe(qsal-5,7-X 2)(NCS)(MeO)] 2 •solv. (X = Cl (1a), Br (2a), I (3a, solv = 1 / 2 MeOH), [Fe 4 (qsal-5,7-X 2) 4 (NCS) 2-(MeO) 2 ]•solv. (X = Br (2b), I (3b; solv = 4CH 2 Cl 2)) by singlecrystal X-ray diffraction analysis. 1a and 2a are isostructural dimers where each Fe III metal ion, showing a distorted octahedral environment, is bound by a N,N,O tridentate (qsal-5,7-X 2) − (X = Cl and Br) ligand, a N-coordinated SCN − anion, and a bridging methanolate anion. 2b and 3b are centrosymmetric tetramers where each Fe III is bound by three nitrogen atoms and three oxygen atoms derived from a tridentate (qsal-5,7-X 2) − (X = Br and I), a SCN − , a bridging methanolate anion, and a bridging μ 2oxy moiety. In 3b, the iodine atoms dominate the packing interactions through the establishment of a halogen-bonding network. The magnetic behavior of 1a−3a dimers and 2b−3b tetramers indicate the presence of strong antiferromagnetic interactions between Fe III centers (S = 5/2), mediated by the alkoxy bridges. Experimental data can be modeled with an isotropic Hamiltonian, H = −2J(S 1 • S 2) for dimers (J = −15 cm −1) and H = −2J(S 2 • S 3) − 2J′(S 1 • S 2 + S 3 • S 4), for tetramers (J = −24 cm −1 , J′ = −11 cm −1). The magnetic behavior of 1a−3a dimers indicates the presence of strong antiferromagnetic interactions between Fe III centers (S = 5/2), mediated by the alkoxy bridges. 2b and 3b show the same magnetic behavior since they contains analogous bridges between paramagnetic centers, but for a linear tetramer. Density functional theory (DFT) calculations, based on hybrid functional mPW1PW paralleled by the Def2SVP all-electron split-valence basis sets, support the experimental results, showing that monomers could possibly show a spin crossover (SCO) behavior, even though the formation of complexes with an even number of metal ions results in the strong antiferromagnetic interactions. Accordingly, broken symmetry DFT calculations carried out on 1a clearly show that the antiferromagnetic coupling of the two HS Fe III centers results in the lowest energy electron configuration of the complex.

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Section: Resultsmentioning

confidence: 99%

Structural Diversity in a New Series of Halogenated Quinolyl Salicylaldimides-Based Fe^III Complexes Showing Solid-State Halogen-Bonding/Halogen···Halogen Interactions

Sahadevan

Cadoni

Monni

et al. 2018

Crystal Growth & Design

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“…Other leaving groups such as aziridines, 83 carbonates, 84 sulfonates, 85-87 thioethers, 88 PMB ether, 89 carbamate 90 were studied and recently applied in total synthesis. The sulfonate groups (Ms or Ts) were used by the groups of Barker, Ghosh and Zhao for the synthesis of Fragransin A 2 , 85 Mandelalide A, 87 and Amphidinolide T3 86 respectively.…”

Section: Scheme 25: Thf Formation By Reductive Cyclizationmentioning

confidence: 99%

Recent advances in the synthesis of tetrahydrofurans and applications in total synthesis

et al. 2016

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Mousseron. His research interests include the total synthesis of oxygenated cyclic and non cyclic metabolites of polyunsaturated fatty acids, mainly leukotrienes, iso-, phyto-and neuroprostanes, as well as dihydroxylated PUFAs and more recently lipophenols and the understanding of the role of such bioactive lipids and lipophenols by developing collaborations with chemists, biochemists, biologists and clinicians across the world. Jean-Marie Galano studied chemistry at Paul Cézanne Université Marseille and obtained his PhD under the supervision of Honoré Monti in 2001. He then moved to the University of Oxford to pursue a postdoctoral fellowship with David H. Hodgson on the development of new methods for the total synthesis of natural products. In October 2005 he joined the CNRS as a Chargé de Recherche at Université of Montpellier. His research focuses on the total synthesis and discovery of new lipid metabolites, and to discover their potential implications in human health. AbstractMany natural products contain tetrahydrofuran (THF) moieties. Those molecules, often biologically active, may be structurally diverse, e.g. cis or trans THF, mono-, di-, tri-or tetrasubstituted on the furan ring. Thus, the construction of THF is of great interest for the community of organic chemists; especially in developing new methodologies, and applying them in the total synthesis of natural products. The aim of this review is to report recent advances in the field of THF synthesis, as well as the application of these methods to the synthesis of bioactive compounds.

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“…Cyclopropyl carbaldehydes and cyclopropyl ketones represent a very useful synthetic tool for the construction of complex molecular structures that have been used in the preparation of bioactive molecules [1,2], building blocks [3][4][5][6] and enantiomerically enriched, strained carbocyclic systems [7][8][9] (Figure 1a). Since the 1970s, several authors have highlighted the synthetic potential of this class of compounds, proposing for their preparation various strategies that mainly involve the use of organolithium reactants in deprotonation procedures involving bis-arylthiopropanes or (3-chloropropyl)(phenyl)sulfane [10][11][12], the deprotonation of the commercially available phenylthiocyclopropane [13,14] and the capture of suitable electrophiles [15] or, alternatively, the cyclopropanation of sulfanylnitriles [16,17] (Figure 1b).…”

Section: Introductionmentioning

confidence: 99%

Continuous-Flow Synthesis of Arylthio-Cyclopropyl Carbonyl Compounds

et al. 2022

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The straightforward, continuous-flow synthesis of cyclopropyl carbaldehydes and ketones has been developed starting from 2-hydroxycyclobutanones and aryl thiols. This acid-catalyzed mediated procedure allows access to the multigram and easily scalable synthesis of cyclopropyl adducts under mild conditions, using reusable Amberlyst-35 as a catalyst. The resins, suitably ground and used for filling steel columns, have been characterized via TGA, ATR, SEM and BET analyses to describe the physical–chemical properties of the packed bed and the continuous-flow system in detail. To highlight the synthetic versatility of the arylthiocyclopropyl carbonyl compounds, a series of selective oxidation reactions have been performed to access sulfoxide and sulfone carbaldehyde cyclopropanes, oxiranes and carboxylic acid derivatives.

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From (Phenylsulfanyl)cycloalkanecarbaldehydes to Optically Active Spirocyclic Tetrahydrofurans: Stereospecific Resolution of Symmetric Aldehydes through (S)‐Proline‐Catalysed Aldol Reaction

Cited by 14 publications

References 91 publications

Structural Diversity in a New Series of Halogenated Quinolyl Salicylaldimides-Based Fe^III Complexes Showing Solid-State Halogen-Bonding/Halogen···Halogen Interactions

Structural Diversity in a New Series of Halogenated Quinolyl Salicylaldimides-Based Fe^III Complexes Showing Solid-State Halogen-Bonding/Halogen···Halogen Interactions

Recent advances in the synthesis of tetrahydrofurans and applications in total synthesis

Continuous-Flow Synthesis of Arylthio-Cyclopropyl Carbonyl Compounds

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From (Phenylsulfanyl)cycloalkanecarbaldehydes to Optically Active Spirocyclic Tetrahydrofurans: Stereospecific Resolution of Symmetric Aldehydes through (S)‐Proline‐Catalysed Aldol Reaction

Cited by 14 publications

References 91 publications

Structural Diversity in a New Series of Halogenated Quinolyl Salicylaldimides-Based FeIII Complexes Showing Solid-State Halogen-Bonding/Halogen···Halogen Interactions

Structural Diversity in a New Series of Halogenated Quinolyl Salicylaldimides-Based FeIII Complexes Showing Solid-State Halogen-Bonding/Halogen···Halogen Interactions

Recent advances in the synthesis of tetrahydrofurans and applications in total synthesis

Continuous-Flow Synthesis of Arylthio-Cyclopropyl Carbonyl Compounds

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Product

Resources

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Structural Diversity in a New Series of Halogenated Quinolyl Salicylaldimides-Based Fe^III Complexes Showing Solid-State Halogen-Bonding/Halogen···Halogen Interactions

Structural Diversity in a New Series of Halogenated Quinolyl Salicylaldimides-Based Fe^III Complexes Showing Solid-State Halogen-Bonding/Halogen···Halogen Interactions