A tutorial review of stereoretentive olefin metathesis based on ruthenium dithiolate catalysts

Daniel S. Müller,
Olivier Baslé and
Marc Mauduit

Review
Published 07 Dec 2018

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1. Graphical Abstract
2. Scheme 1: Synthesis of first Ru-dithiolate metathesis catalysts.
  
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3. Figure 1: Most efficient Ru-dithiolate catalysts for stereoretentive olefin metathesis with Z- and E-alkenes ...
  
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4. Figure 2: Selected examples of sterically or electronically modified ruthenium dithiolate complexes.
  
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5. Figure 3: Model for stereoretentive metathesis proposed by Pederson and Grubbs [3].
  
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6. Figure 4: Decrease in the benzylidene signal over time upon reaction with (E)-2-hexenyl acetate.
  
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7. Scheme 2: Selected applications, part 1.
  
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8. Scheme 3: Selected applications, part 2.
  
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9. Figure 5: Catalyst loading required for different types of metathesis reactions.
  
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10. Scheme 4: Proposed catalyst decomposition pathway occurring via attack of the electron-rich sulfide into meth...
  
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11. Scheme 5: In situ methylene capping strategy for stereoretentive metathesis.
  
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12. Scheme 6: Stereoretentive cross-metathesis with (Z)-butene (Z-25) as in situ methylene capping agent; selecte...
  
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13. Scheme 7: Cross metathesis with Z- and E-trisubstituted allylic alcohols.
  
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14. Scheme 8: In situ synthesis of Ru-3 and application thereof in the cross-metathesis of 12 and 50.
  
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15. Figure 6: Examples of biologically active and fragrance molecules synthesized by stereoretentive metathesis.
  
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Beilstein J. Org. Chem. 2018, 14, 2999–3010, doi:10.3762/bjoc.14.279

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Ring-closing-metathesis-based synthesis of annellated coumarins from 8-allylcoumarins

Christiane Schultze and
Bernd Schmidt

Full Research Paper
Published 05 Dec 2018

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1. Graphical Abstract
2. Figure 1: Illustration of coumarin taxonomy.
  
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3. Scheme 1: Synthesis of oxepin-2-one-annellated coumarins 13 by RCM of acrylates 12.
  
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4. Scheme 2: Attempted synthesis of pyran-2-one-annellated coumarin 15d via isomerization-RCM.
  
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5. Scheme 3: Synthesis of aza-annellated coumarin 21 and attempted synthesis of indole 22.
  
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Beilstein J. Org. Chem. 2018, 14, 2991–2998, doi:10.3762/bjoc.14.278

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Volatiles from the hypoxylaceous fungi Hypoxylon griseobrunneum and Hypoxylon macrocarpum

Jan Rinkel,
Alexander Babczyk,
Tao Wang,
Marc Stadler and
Jeroen S. Dickschat

Full Research Paper
Published 04 Dec 2018

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1. Graphical Abstract
2. Figure 1: Structures of fungal volatiles. Trichodiene (1), aristolochene (2), (R)-oct-1-en-3-ol (3), 3,4-dime...
  
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3. Figure 2: Total ion chromatogram of a CLSA headspace extract from Hypoxylon griseobrunneum MUCL 53754. Peak n...
  
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4. Figure 3: Volatiles from Hypoxylon griseobrunneum.
  
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5. Figure 4: EI mass spectra of A) 2,4,5-trimethylanisole (24), B) the coeluting mixture of 3,4-dimethylanisole (...
  
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6. Scheme 1: Synthesis of trimethylanisoles 24 and 24d.
  
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7. Scheme 2: Hypothetical biosynthesis of 24. ACP: acyl carrier protein, AT: acyl transferase, KR: ketoreductase...
  
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8. Figure 5: Biosynthesis of 24. Feeding of (methyl-²H₃)methionine resulted in the incorporation of labelling in...
  
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9. Scheme 3: Hypothetical biosynthesis of 25 and 26.
  
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10. Figure 6: Total ion chromatogram of a CLSA headspace extract from Hypoxylon macrocarpum STMA 130423. Peak num...
  
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11. Figure 7: Volatiles from Hypoxylon macrocarpum.
  
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12. Figure 8: EI mass spectra of A) 3,4-dimethoxybenzaldehyde (42), B) 3,4,5-trimethoxytoluene (44), and C) 2,4,5...
  
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13. Scheme 4: Synthesis of 2,3,4-trimethoxytoluene (44a).
  
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Beilstein J. Org. Chem. 2018, 14, 2974–2990, doi:10.3762/bjoc.14.277

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N-Acylated amino acid methyl esters from marine Roseobacter group bacteria

Hilke Bruns,
Lisa Ziesche,
Nargis Khakin Taniwal,
Laura Wolter,
Thorsten Brinkhoff,
Jennifer Herrmann,
Rolf Müller and
Stefan Schulz

Full Research Paper
Published 03 Dec 2018

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1. Graphical Abstract
2. Figure 1: N-Acylhomoserine lactones 1 (Z7-C14:1-AHL) and N-acylalanine methyl esters 2 (Z9-C16:1-NAME) occurr...
  
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3. Figure 2: Total ion chromatogram (TIC) of an XAD extract of Roseovarius sp. D12_1.68. AHLs, NAMEs and related...
  
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4. Scheme 1: Synthesis of iso-C15:0-NAME (6). DMAP: 4-dimethylaminopyridine, EDC: 1-ethyl-3-(3-dimethylaminoprop...
  
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5. Figure 3: Mass spectrum of natural compound D, N-(13-methyltetradecanoyl)alanine methyl ester (iso-C15:0-NAME...
  
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6. Figure 4: Mass spectra of natural compounds a) K (7, C16:0-NABME), b) J (8, C16:1-NABME), and c) N (9, C16:1-...
  
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7. Scheme 2: Synthesis of N-acylated amino acid methyl esters 7–11. AAME: amino acid methyl ester.
  
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8. Figure 5: TIC of an XAD extract of Loktanella sp. F14. Compound S is a minor component within the broad peak.
  
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9. Figure 6: Mass spectra of natural compounds a) R (11, C16:1-NAGME) and b) S (10, C16:0-NAGME).
  
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10. Figure 7: EI mass spectrometric fragmentation of N-acylated amino acid derivatives. The ions w–z allow identi...
  
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11. Figure 8: MS² spectra in ESI positive mode of a) Z9-16OH-C16:1-NAME with [M + H − H₂O]⁺ 356, b) Z9-C16:1-NABM...
  
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Beilstein J. Org. Chem. 2018, 14, 2964–2973, doi:10.3762/bjoc.14.276

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The activity of indenylidene derivatives in olefin metathesis catalysts

Maria Voccia,
Steven P. Nolan,
Luigi Cavallo and
Albert Poater

Full Research Paper
Published 30 Nov 2018

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1. Graphical Abstract
2. Scheme 1: Catalysts studied by DFT calculations.
  
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3. Scheme 2: Precatalyst initiation in olefin metathesis (L = NHC ligand).
  
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4. Figure 1: Topographic steric maps (plane xy) of the NHC ligands of species I for the studied SIMes–Ru complex...
  
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5. Figure 2: Intermediate II for catalysts a) 1 and b) 5 (important bond lengths are given in Å).
  
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Beilstein J. Org. Chem. 2018, 14, 2956–2963, doi:10.3762/bjoc.14.275

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Stereodivergent approach in the protected glycal synthesis of L-vancosamine, L-saccharosamine, L-daunosamine and L-ristosamine involving a ring-closing metathesis step

Pierre-Antoine Nocquet,
Aurélie Macé,
Frédéric Legros,
Jacques Lebreton,
Gilles Dujardin,
Sylvain Collet,
Arnaud Martel,
Bertrand Carboni and
François Carreaux

Full Research Paper
Published 29 Nov 2018

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1. Graphical Abstract
2. Figure 1: N,N-Dimethyl-L-vancosamine as substructure of kidamycin and pluramycin.
  
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3. Figure 2: Glycals as relevant scaffolds for constructing aryl C-glycosidic linkage.
  
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4. Figure 3: Strategy including a ring-closing metathesis of vinyl ethers as key step for the preparation of sev...
  
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5. Scheme 1: Evans aldol reaction for the preparation of diastereomeric compounds 13a and 13b.
  
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6. Scheme 2: Alternative preparation of 13b based on a diastereoselective allylboration.
  
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7. Scheme 3: O-Vinylation-ring-closing metathesis sequence for access to 3-amino glycals.
  
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8. Scheme 4: Synthesis of key intermediate 23 for the C-3 unbranched amino glycals preparation.
  
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9. Scheme 5: Access to diastereoisomeric compounds 3 and 4 from 23.
  
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Beilstein J. Org. Chem. 2018, 14, 2949–2955, doi:10.3762/bjoc.14.274

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1,8-Bis(dimethylamino)naphthyl-2-ketimines: Inside vs outside protonation

A. S. Antonov,
A. F. Pozharskii,
P. M. Tolstoy,
A. Filarowski and
O. V. Khoroshilova

Full Research Paper
Published 28 Nov 2018

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1. Graphical Abstract
2. Scheme 1: Protonation of DMAN.
  
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3. Scheme 2: Protonation equilibria for 2 and 3.
  
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4. Scheme 3: Protonation of imine 4a with perchloric acid.
  
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5. Scheme 4: Synthesis of investigated substrates (yields obtained by paths a and b are denoted by a correspondi...
  
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6. Scheme 5: Preparation of protonated forms of imines 4–7.
  
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7. Figure 1: C=NH Signal regions of temperature-depending ¹H NMR spectra for compounds 4a–7a, acetone-d₆.
  
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8. Scheme 6: E/Z-Isomerisation of ketimines 4a–7a.
  
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9. Figure 2: Molecular structure of imines 6a (a) and 4a (b). The H···O distance for 6a is shown.
  
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10. Figure 3: Optimised geometry and energy difference ΔE = E_E – E_Z (kcal/mol) for imines 4a–7a (B3LYP/6-311+G(d,...
  
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11. Figure 4: ¹H NMR spectra of imines 4b–7b (4b’–7b’) in DMSO-d₆, 25 °C (the signals of the forms protonated at ...
  
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12. Scheme 7: Switching of protonation sites in imines 4b–7b.
  
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13. Figure 5: Optimised geometries and energy differences ΔE = E_b’ – E_b (kcal/mol) for different sites of protona...
  
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14. Figure 6: Molecular structure of protonated imines 4a·HClO₄ (a) and 6b·EtOH (b).
  
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15. Scheme 8: Protonation of the out-inverted dialkylamino group.
  
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16. Scheme 9: Examples of proton sponges with stabilised in,out-conformation.
  
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17. Figure 7: C=NH₂⁺ Signal regions of temperature-depending spectra for compounds 4c–7c, acetone-d₆.
  
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18. Figure 8: Molecular structure of dication 6с.
  
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Beilstein J. Org. Chem. 2018, 14, 2940–2948, doi:10.3762/bjoc.14.273

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MoO₃ on zeolites MCM-22, MCM-56 and 2D-MFI as catalysts for 1-octene metathesis

Hynek Balcar,
Martin Kubů,
Naděžda Žilková and
Mariya Shamzhy

Full Research Paper
Published 27 Nov 2018

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1. Graphical Abstract
2. Scheme 1: 1-Octene metathesis reaction.
  
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3. Figure 1: A,B,C,D: XRD patterns of parent supports and catalysts used. Asterisk marks MoO₃.
  
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4. Figure 2: Conversion vs time curves for 1-octene metathesis over 6MoO₃/MCM-22(28) and 6MoO₃/SBA-15. Neat 1-oc...
  
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5. Figure 3: Conversion vs time curves for the 1-octene metathesis over 6MoO₃/MCM-56(13). Neat 1-octene, 1-octen...
  
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6. Figure 4: Conversion vs time curves for 1-octene metathesis over 6MoO₃/2D-MFI(26) and 6MoO3/HZSM-5(25). Neat ...
  
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7. Figure 5: Conversion to oligomers for 1-octene over MCM-22(28) and MCM-22(70) (a) and conversion to oligomers...
  
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Beilstein J. Org. Chem. 2018, 14, 2931–2939, doi:10.3762/bjoc.14.272

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Green synthesis of new chiral 1-(arylamino)imidazo[2,1-a]isoindole-2,5-diones from the corresponding α-amino acid arylhydrazides in aqueous medium

Nadia Bouzayani,
Jamil Kraїem,
Sylvain Marque,
Yakdhane Kacem,
Abel Carlin-Sinclair,
Jérôme Marrot and
Béchir Ben Hassine

Full Research Paper
Published 26 Nov 2018

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1. Graphical Abstract
2. Figure 1: Chemical structures of analogues.
  
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3. Scheme 1: Strategy for the formation of 1-(arylamino)-1H-imidazo[2,1-a]isoindole-2,5(3H,9bH)-diones.
  
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4. Scheme 2: Synthesis of the starting (L)-α-amino acid phenylhydrazides and 4-chlorophenylhydrazides 3a–m under...
  
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5. Scheme 3: Cyclocondensation of 2-formylbenzoic acid (4) with (L)-alanine phenylhydrazide (3a).
  
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6. Scheme 4: Synthesis of the nitrogenated tricyclic compounds 5a–m. Diastereoisomeric (dr) and enantiomeric (er...
  
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7. Figure 2: NOEs correlation showing the stereochemistry of the compound 5a.
  
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8. Figure 3: X-ray crystal structure of 5f shown at the 30% probability level.
  
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9. Scheme 5: Proposed partial mechanism with a selectivity model.
  
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Beilstein J. Org. Chem. 2018, 14, 2923–2930, doi:10.3762/bjoc.14.271

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Copper(I)-catalyzed tandem reaction: synthesis of 1,4-disubstituted 1,2,3-triazoles from alkyl diacyl peroxides, azidotrimethylsilane, and alkynes

Muhammad Israr,
Changqing Ye,
Munira Taj Muhammad,
Yajun Li and
Hongli Bao

Full Research Paper
Published 23 Nov 2018

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1. Graphical Abstract
2. Scheme 1: General methods for the synthesis of triazoles.
  
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3. Scheme 2: Substrate scope of the terminal alkynes. Conditions: 1 (0.5 mmol), 2a (0.75 mmol), TMSN₃ (0.75 mmol...
  
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4. Scheme 3: Substrate scope of the alkyl diacyl peroxides. Conditions: 1a (0.5 mmol), 2 (0.75 mmol), TMSN₃ (0.7...
  
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5. Scheme 4: Preliminary mechanistic studies.
  
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6. Scheme 5: Plausible reaction mechanism.
  
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Beilstein J. Org. Chem. 2018, 14, 2916–2922, doi:10.3762/bjoc.14.270

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