Progress in metathesis chemistry II

Editor: Prof. Karol Grela
Uniwersytet Warszawski

Five years have passed since the first publication of the Thematic Series on Olefin Metathesis in the Beilstein Journal of Organic Chemistry. During these years the research continued to progress at full speed. Astute readers of this Thematic Series can easily see that a great number of studies in this field have advanced from the basic research phase to the commercial application stage. While new, active and more selective catalysts that solve some longstanding limitations are still being developed, a growing number of projects deal only with applications using olefin metathesis as one of many stock transformations.

Progress in metathesis chemistry II

Karol Grela

Editorial
Published 15 Sep 2015

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Beilstein J. Org. Chem. 2015, 11, 1639–1640, doi:10.3762/bjoc.11.179

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Hybrid macrocycle formation and spiro annulation on cis-syn-cis-tricyclo[6.3.0.0^2,6]undeca-3,11-dione and its congeners via ring-closing metathesis

Sambasivarao Kotha,
Ajay Kumar Chinnam and
Rashid Ali

Full Research Paper
Published 06 Jul 2015

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1. Graphical Abstract
2. Figure 1: Natural and non-natural products containing quinane systems.
  
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3. Figure 2: Quinane building blocks (1–3) and metathetic catalyst used in our strategy.
  
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4. Scheme 1: Synthesis of tricyclic diones 5 and 2.
  
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5. Figure 3: Retrosynthetic approach to aza-polyquinane 6 and spiro-polyquinane 7.
  
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6. Scheme 2: Synthesis of the diindole derivative 9 Reagents and conditions: (i) TA:DMU, PhNHNH₃Cl, 70 °C, 6 h, ...
  
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7. Scheme 3: Synthesis of the macrocyclic aza-polyquinane derivative 6. Reagents and conditions: (i) NaH, allyl ...
  
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8. Scheme 4: Synthesis of the spiro-polyquinane 7. Reagents and conditions: (i) NaH, allyl bromide, THF, rt, 24 ...
  
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9. Scheme 5: General strategy to bis-spirocycles via RCM.
  
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Beilstein J. Org. Chem. 2015, 11, 1123–1128, doi:10.3762/bjoc.11.126

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Design and synthesis of fused polycycles via Diels–Alder reaction and ring-rearrangement metathesis as key steps

Sambasivarao Kotha and
Ongolu Ravikumar

Full Research Paper
Published 27 Jul 2015

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1. Graphical Abstract
2. Figure 1: Commercially available ruthenium catalysts used in RRM metathesis.
  
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3. Figure 2: Crystal structure of 5 with thermal ellipsoids drawn at 50% probability level.
  
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4. Scheme 1: Synthesis of hexacyclic compound 6a by using an RRM approach.
  
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5. Scheme 2: Synthesis of hexacyclic compound 11 by using an RRM route.
  
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Beilstein J. Org. Chem. 2015, 11, 1259–1264, doi:10.3762/bjoc.11.140

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Spiro annulation of cage polycycles via Grignard reaction and ring-closing metathesis as key steps

Sambasivarao Kotha,
Mohammad Saifuddin,
Rashid Ali and
Gaddamedi Sreevani

Full Research Paper
Published 05 Aug 2015

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1. Graphical Abstract
2. Figure 1: Structures of diverse biologically as well as theoretically interesting molecules.
  
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3. Figure 2: Retrosynthetic analysis of bis-spiro-pyrano cage compound 7.
  
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4. Scheme 1: Synthesis of hexacyclic cage dione 10.
  
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5. Scheme 2: Synthesis of tetrahydrofuran-based cage compounds 12 and 13.
  
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6. Figure 3: (a)Optimized structure of 12, (b) optimized structure of 13.
  
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7. Scheme 3: Synthesis di-allyl cage compound 11.
  
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8. Scheme 4: Synthesis of spiro-pyrano cage molecules 7 and 17.
  
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9. Figure 4: (a) Optimized structure of 18, (b) optimized structure of 7.
  
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10. Scheme 5: Synthesis of octacyclic cage compound 18 via intramolecular DA reaction.
  
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11. Scheme 6: Attempted synthesis to cage compound 20.
  
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Beilstein J. Org. Chem. 2015, 11, 1367–1372, doi:10.3762/bjoc.11.147

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Design and synthesis of polycyclic sulfones via Diels–Alder reaction and ring-rearrangement metathesis as key steps

Sambasivarao Kotha and
Rama Gunta

Full Research Paper
Published 06 Aug 2015

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1. Graphical Abstract
2. Figure 1: Retrosynthetic approach to polycyclic sulfones.
  
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3. Scheme 1: Preparation of the sulfone 6 via oxidation.
  
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4. Scheme 2: Synthesis of alkenylated sulfone derivatives.
  
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5. Scheme 3: Synthesis of 10 by RRM of 2a.
  
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6. Scheme 4: Synthesis of 1b using RRM.
  
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7. Scheme 5: RRM of the dipentenyl sulfone 2c.
  
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8. Scheme 6: RRM of the dihexenyl sulfone 2d.
  
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Beilstein J. Org. Chem. 2015, 11, 1373–1378, doi:10.3762/bjoc.11.148

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Cross-metathesis reaction of α- and β-vinyl C-glycosides with alkenes

Ivan Šnajdr,
Kamil Parkan,
Filip Hessler and
Martin Kotora

Full Research Paper
Published 10 Aug 2015

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1. Graphical Abstract
2. Scheme 1: Synthesis of vinyl C-deoxyribosides α-2 and β-2.
  
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3. Figure 1: Alkenes 3 used in cross-metathesis reactions with 2.
  
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4. Scheme 2: Hydrogenation of β-4b–β-4d to β-5b–β-5d.
  
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5. Scheme 3: Deprotection of β-4e and β-5b to β-6e and β-7b.
  
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Beilstein J. Org. Chem. 2015, 11, 1392–1397, doi:10.3762/bjoc.11.150

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Consequences of the electronic tuning of latent ruthenium-based olefin metathesis catalysts on their reactivity

Karolina Żukowska,
Eva Pump,
Aleksandra E. Pazio,
Krzysztof Woźniak,
Luigi Cavallo and
Christian Slugovc

Full Research Paper
Published 20 Aug 2015

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1. Graphical Abstract
2. Figure 1: Selected ruthenium-based complexes.
  
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3. Scheme 1: trans–cis Isomerization.
  
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4. Scheme 2: Synthesis of the ligand precursors.
  
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5. Scheme 3: Synthesis of the ruthenium complexes.
  
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6. Figure 2: ADPs (atomic displacement parameters) and atoms labeling of the first molecule in the asymmetric pa...
  
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7. Figure 3: Superposition of the asymmetric parts of units’ cells in both investigated structures: an example o...
  
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8. Figure 4: Energy profile of trans–cis isomerization, modelled in CH₂Cl₂, (ΔE in kcal/mol). Geometry optimizat...
  
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9. Scheme 4: Possible reaction pathways of 16.
  
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10. Figure 5: Time/conversion plots for the transformation of 16 catalyzed by 5 mol % of the trans isomers of tra...
  
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11. Figure 6: Composition of a reaction mixture after subjecting 16 to 5 mol % cis-5a in xylene, 140 °C. Lines ar...
  
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12. Figure 7: Monomers utilized in model ROMP reactions.
  
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13. Figure 8: Number-average molecular weight (M_n) of poly-21 prepared with initiators 5a, 14 and 15 plotted agai...
  
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14. Figure 9: STA analysis of polymerization of 22 (left) and 23 (right), initiated by 5a, 14 and 15. Reaction co...
  
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Beilstein J. Org. Chem. 2015, 11, 1458–1468, doi:10.3762/bjoc.11.158

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Thermal properties of ruthenium alkylidene-polymerized dicyclopentadiene

Yuval Vidavsky,
Yotam Navon,
Yakov Ginzburg,
Moshe Gottlieb and
N. Gabriel Lemcoff

Full Research Paper
Published 21 Aug 2015

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1. Graphical Abstract
2. Figure 1: DCPD (1) and ruthenium benzylidene catalyst 2.
  
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3. Scheme 1: ROMP of dicyclopentadiene by a ruthenium alkylidene initiator.
  
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4. Figure 2: Top: DSC plot of PDCPD 24 hours after polymerization. Blue line: 1st heating–cooling cycle. Black l...
  
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5. Figure 3: Change in T_g for a representative PDCPD sample as a function of time.
  
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6. Figure 4: Intensity of exothermic peak as a function of rest time at room temperature for different samples.
  
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7. Figure 5: Peak intensity as function of age. Samples were analyzed every two weeks. The abnormal low intensit...
  
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8. Figure 6: Resting temperature effect. Blue columns: resting at room temperature. Orange columns: resting at −...
  
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9. Figure 7: Top: Sample after 1 week with ethyl vinyl ether. Bottom: Sample after 1 week with diethyl ether.
  
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Graphical Abstract

Beilstein J. Org. Chem. 2015, 11, 1469–1474, doi:10.3762/bjoc.11.159

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Tandem cross enyne metathesis (CEYM)–intramolecular Diels–Alder reaction (IMDAR). An easy entry to linear bicyclic scaffolds

Javier Miró,
María Sánchez-Roselló,
Álvaro Sanz,
Fernando Rabasa,
Carlos del Pozo and
Santos Fustero

Full Research Paper
Published 25 Aug 2015

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1. Graphical Abstract
2. Scheme 1: Tandem cross enyne metathesis–intramolecular Diels–Alder reaction.
  
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3. Scheme 2: Stereochemical outcome of the IMDAR.
  
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4. Scheme 3: Preparation of starting materials 8.
  
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5. Figure 1: Determination of the relative stereochemistry on compounds 10b.
  
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Beilstein J. Org. Chem. 2015, 11, 1486–1493, doi:10.3762/bjoc.11.161

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Synthesis of a tricyclic lactam via Beckmann rearrangement and ring-rearrangement metathesis as key steps

Sambasivarao Kotha,
Ongolu Ravikumar and
Jadab Majhi

Full Research Paper
Published 27 Aug 2015

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1. Graphical Abstract
2. Figure 1: Retrosynthetic analysis of tricyclic amide 1.
  
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3. Scheme 1: Synthesis of tricyclic ketone 4.
  
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4. Scheme 2: Beckmann rearrangement of oximes 8a and 8b.
  
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5. Scheme 3: Beckmann rearrangement reaction in a single step.
  
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6. Scheme 4: Synthesis of ring-rearrangement precursors.
  
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7. Scheme 5: Synthesis of Beckmann rearrangement precursors.
  
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8. Scheme 6: Beckmann rearrangement of oxime isomers 11a and 11b.
  
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9. Figure 2: Molecular crystal structure of compound 11b.
  
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10. Scheme 7: Synthesis of aza tricyclic compound 1 by RRM.
  
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Beilstein J. Org. Chem. 2015, 11, 1503–1508, doi:10.3762/bjoc.11.163

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Design and synthesis of hybrid cyclophanes containing thiophene and indole units via Grignard reaction, Fischer indolization and ring-closing metathesis as key steps

Sambasivarao Kotha,
Ajay Kumar Chinnam and
Mukesh E. Shirbhate

Full Research Paper
Published 31 Aug 2015

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1. Graphical Abstract
2. Figure 1: Retrosynthetic approach to hybrid cyclophane derivative 1.
  
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3. Scheme 1: Attempted synthesis of thiophenophane derivative 2.
  
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4. Scheme 2: Synthesis of hybrid cyclophane 1.
  
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5. Figure 2: The molecular crystal structure of 1 with 50% probability [41].
  
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6. Scheme 3: Attempted synthesis of thiophenophane derivative 2a.
  
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7. Scheme 4: Synthesis of cyclophane 1a with a thiophene and an indole moiety.
  
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Beilstein J. Org. Chem. 2015, 11, 1514–1519, doi:10.3762/bjoc.11.165

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Ruthenium indenylidene “1^st generation” olefin metathesis catalysts containing triisopropyl phosphite

Stefano Guidone,
Fady Nahra,
Alexandra M. Z. Slawin and
Catherine S. J. Cazin

Full Research Paper
Published 01 Sep 2015

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1. Graphical Abstract
2. Figure 1: Examples of ruthenium complexes used in olefin metathesis reactions.
  
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3. Scheme 1: Synthesis of the mixed phosphine/phosphite complex 1.
  
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4. Figure 2: Molecular structure of mixed phosphine/phosphite complex 1. Hydrogen atoms are omitted for clarity.
  
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5. Scheme 2: Synthesis of the bis-phosphite complex 2.
  
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6. Figure 3: Molecular structure of 2 and the ylide 3. Hydrogen atoms and solvent molecules are omitted for clar...
  
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7. Figure 4: Reaction profiles of mixed phosphine/phosphite 1 and phosphine-based Ind-I in the RCM of 4 (lines a...
  
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Beilstein J. Org. Chem. 2015, 11, 1520–1527, doi:10.3762/bjoc.11.166

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Latent ruthenium–indenylidene catalysts bearing a N-heterocyclic carbene and a bidentate picolinate ligand

Thibault E. Schmid,
Florian Modicom,
Adrien Dumas,
Etienne Borré,
Loic Toupet,
Olivier Baslé and
Marc Mauduit

Full Research Paper
Published 03 Sep 2015

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1. Graphical Abstract
2. Scheme 1: Synthesis of [NHC(picolinate)RuCl(indenylidene)] complexes 2 and 4a.
  
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3. Scheme 2: Synthesis of complex 4a and 4b from (SIPr)(pyridine)RuCl₂(indenylidene) (5).
  
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4. Figure 1: Solid-state structure of complex 4a from single crystal X-ray diffraction. Hydrogens have been omit...
  
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5. Figure 2: Olefin metathesis profiles in response to TFA equivalents.
  
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6. Figure 3: Comparison of olefin metathesis profiles for catalysts 2, 4a and 4b after activation with 150 equiv...
  
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7. Figure 4: Influence of various acids for the activation of 4a in the RCM of DEDAM.
  
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Beilstein J. Org. Chem. 2015, 11, 1541–1546, doi:10.3762/bjoc.11.169

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Grubbs–Hoveyda type catalysts bearing a dicationic N-heterocyclic carbene for biphasic olefin metathesis reactions in ionic liquids

Maximilian Koy,
Hagen J. Altmann,
Benjamin Autenrieth,
Wolfgang Frey and
Michael R. Buchmeiser

Full Research Paper
Published 15 Sep 2015

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1. Graphical Abstract
2. Figure 1: Catalysts synthesized by post-assembly tagging (Mes = mesitylene).
  
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3. Scheme 1: Improved synthesis of Ru-1 and quarternization with methyl trifluoromethanesulfonate to Ru-2.
  
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4. Figure 2: Single crystal X-ray structure of Ru-2. Co-solvent and disordered triflates have been omitted for c...
  
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5. Figure 3: Monomers used for biphasic ROMP reactions.
  
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6. Scheme 2: Recycling of Ru-2 for continuous ROMP reactions.
  
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Beilstein J. Org. Chem. 2015, 11, 1632–1638, doi:10.3762/bjoc.11.178

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Design and synthesis of propellane derivatives and oxa-bowls via ring-rearrangement metathesis as a key step

Sambasivarao Kotha and
Rama Gunta

Full Research Paper
Published 24 Sep 2015

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1. Graphical Abstract
2. Figure 1: RRM route to propellane derivatives and oxa-bowls.
  
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3. Scheme 1: Synthesis of the oxa-bowl 1a via RRM.
  
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4. Scheme 2: Synthesis of RRM products 1b and 5a starting from DA adduct 3b.
  
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5. Scheme 3: Synthesis of the hexacyclic compound 1c using RRM.
  
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6. Scheme 4: Synthesis of the propellane/oxa-bowl hybrids 7a,b via RRM.
  
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Beilstein J. Org. Chem. 2015, 11, 1727–1731, doi:10.3762/bjoc.11.188

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A comprehensive study of olefin metathesis catalyzed by Ru-based catalysts

Albert Poater and
Luigi Cavallo

Full Research Paper
Published 29 Sep 2015

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1. Graphical Abstract
2. Scheme 1: Mechanism of the olefin metathesis.
  
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3. Scheme 2: Possible side or bottom mechanism of the insertion of the olefin.
  
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4. Scheme 3: Ruthenium catalysts, bottom-bound (a) or side-bound (b and c).
  
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5. Scheme 4: Studied systems.
  
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6. Figure 1: a) Naked 14e species for system 9 (distance in Å). b) trans (T); c) cis(S) (C(S)); and d) cis(O) (C...
  
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7. Figure 2: Coordinated species for species a) 13a and b) 13b.
  
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8. Figure 3: Naked 14e species for system 14 with the O atom of the substrate coordinated to the Ru center (dist...
  
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9. Figure 4: System 9 with a Ru^…F interaction in the cis and trans geometries, parts a and b, respectively (dist...
  
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10. Figure 5: Representative geometries of the metallacycles 7 and 15, parts a and b, respectively (distance in Å...
  
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11. Figure 6: Energy profiles for systems 1 and 14.
  
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12. Figure 7: Energy profiles for systems 7 and 16.
  
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13. Figure 8: Metallocycle and cyclopropane formation energy profile (energies in kcal/mol).
  
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Beilstein J. Org. Chem. 2015, 11, 1767–1780, doi:10.3762/bjoc.11.192

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Cross-metathesis of polynorbornene with polyoctenamer: a kinetic study

Yulia I. Denisova,
Maria L. Gringolts,
Alexander S. Peregudov,
Liya B. Krentsel,
Ekaterina A. Litmanovich,
Arkadiy D. Litmanovich,
Eugene Sh. Finkelshtein and
Yaroslav V. Kudryavtsev

Full Research Paper
Published 01 Oct 2015

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1. Graphical Abstract
2. Figure 1: Dependences of the (blue) PCOE and (green) PNB mean hydrodynamic radius in CHCl₃ on the (a) light ...
  
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3. Figure 2: Hydrodynamic radius distributions (normalized by their maximum values) in the CHCl₃ solutions of (b...
  
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4. Figure 3: Stability of the primary carbene [Ru]=CHPh in the pure solvent (CDCl₃).
  
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5. Scheme 1: Formation of polyoctenamer-bound carbene by the interaction of Gr-1 with PCOE.
  
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6. Figure 4: (a) Dependences of the normalized (red) [Ru]=CHPh and (blue) [Ru]=PCOE carbene concentrations on ti...
  
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7. Scheme 2: Formation of polynorbornene-bound carbene by the interaction of Gr-1 with PNB.
  
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8. Figure 5: (a) Dependences of the normalized (red) [Ru]=CHPh and (green) [Ru]=PNB carbene concentrations on ti...
  
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9. Scheme 3: Elementary cross-metathesis reactions in the mixture of PCOE with PNB.
  
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10. Figure 6: Dependences of the normalized (red) primary, (blue) PCOE, and (green) PNB carbene concentrations an...
  
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11. Figure 7: The kinetics of NB-COE dyads formation under mixing conditions for the systems with (red) c_in/c_p = ...
  
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12. Figure 8: The ¹H NMR spectrum recorded after 10 min of the reaction between PCOE and Gr-1 at the initial conc...
  
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13. Figure 9: The ¹H NMR spectrum recorded after 653 min of the reaction between PNB and Gr-1 at the initial conc...
  
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14. Figure 10: The ¹H NMR spectrum recorded after 24 h of the reaction between PCOE, PNB, and Gr-1 at the initial ...
  
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15. Figure 11: The ¹³C NMR spectrum recorded after 8 h of the reaction between PCOE, PNB, and Gr-1 at the initial ...
  
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Beilstein J. Org. Chem. 2015, 11, 1796–1808, doi:10.3762/bjoc.11.195

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Nitro-Grela-type complexes containing iodides – robust and selective catalysts for olefin metathesis under challenging conditions

Andrzej Tracz,
Mateusz Matczak,
Katarzyna Urbaniak and
Krzysztof Skowerski

Full Research Paper
Published 06 Oct 2015

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1. Graphical Abstract
2. Figure 1: The diversity of Hoveyda-type complexes (Mes – 2,4,6-trimethylphenyl, DIPP – 2,6-diisopropylphenyl)....
  
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3. Scheme 1: Modifications of the 2^nd generation alkylidene complexes.
  
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4. Scheme 2: Synthesis of iodide-containing nitro-Grela type catalysts.
  
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5. Figure 2: Reaction profiles for RCM of DEDAM; toluene, 0.2 M, 18 °C, [Ru] 0.15 mol %; conversion determined b...
  
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6. Figure 3: RCM of 1 (toluene, 0.05 M, 25 °C, [Ru] 0.01 mol %); blue diamonds – original (pre)catalysts; red sq...
  
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7. Figure 4: RCM of 1 (toluene, 0.05 M, 25 °C, [Ru] 0.01 mol %): top – productive RCM and possible non-productiv...
  
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Beilstein J. Org. Chem. 2015, 11, 1823–1832, doi:10.3762/bjoc.11.198

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Recent applications of ring-rearrangement metathesis in organic synthesis

Sambasivarao Kotha,
Milind Meshram,
Priti Khedkar,
Shaibal Banerjee and
Deepak Deodhar

Review
Published 07 Oct 2015

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1. Graphical Abstract
2. Figure 1: Ruthenium alkylidene catalysts used in RRM processes.
  
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3. Figure 2: General representation of various RRM processes.
  
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4. Figure 3: A general mechanism for RRM process.
  
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5. Scheme 1: RRM of cyclopropene systems.
  
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6. Scheme 2: RRM of cyclopropene with catalyst 2. (i) catalyst 2 (2.5 mol %), ethylene (24, 1 atm), (ii) toluene...
  
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7. Scheme 3: RRM of various cyclopropene derivatives with catalyst 2. (i) catalyst 2 (2.5 mol %), CH₂Cl₂ (c = 0....
  
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8. Scheme 4: RRM of substituted cyclopropene system with catalyst 2.
  
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9. Scheme 5: RRM of cyclobutene system with catalyst 2.
  
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10. Scheme 6: RRM approach to various bicyclic compounds.
  
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11. Scheme 7: RRM approach to erythrina alkaloid framework.
  
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12. Scheme 8: ROM–RCM sequence to lactone derivatives.
  
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13. Scheme 9: RRM protocol towards the synthesis of lactone derivative 58.
  
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14. Scheme 10: RRM protocol towards the asymmetric synthesis of asteriscunolide D (61).
  
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15. Scheme 11: RRM strategy towards the synthesis of various macrolide rings.
  
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16. Scheme 12: RRM protocol to dipiperidine system.
  
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17. Scheme 13: RRM of cyclopentene system to generate the cyclohexene systems.
  
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18. Scheme 14: RRM of cyclopentene system 74.
  
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19. Scheme 15: RRM approach to compound 79.
  
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20. Scheme 16: RRM approach to spirocycles.
  
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21. Scheme 17: RRM approach to bicyclic dihydropyrans.
  
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22. Scheme 18: RCM–ROM–RCM cascade using non strained alkenyl heterocycles.
  
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23. Scheme 19: First ROM–RCM–ROM–RCM cascade for the synthesis of trisaccharide 97.
  
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24. Scheme 20: RRM of cyclohexene system.
  
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25. Scheme 21: RRM approach to tricyclic spirosystem.
  
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26. Scheme 22: RRM approach to bicyclic building block 108a.
  
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27. Scheme 23: ROM–RCM protocol for the synthesis of the bicyclo[3.3.0]octene system.
  
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28. Scheme 24: RRM protocol to bicyclic enone.
  
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29. Scheme 25: RRM protocol toward the synthesis of the tricyclic system 118.
  
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30. Scheme 26: RRM approach toward the synthesis of the tricyclic enones 122a and 122b.
  
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31. Scheme 27: Synthesis of tricyclic and tetracyclic systems via RRM protocol.
  
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32. Scheme 28: RRM protocol towards the synthesis of tetracyclic systems.
  
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33. Scheme 29: RRM of the propargylamino[2.2.1] system.
  
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34. Scheme 30: RRM of highly decorated bicyclo[2.2.1] systems.
  
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35. Scheme 31: RRM protocol towards fused tricyclic compounds.
  
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36. Scheme 32: RRM protocol to functionalized tricyclic systems.
  
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37. Scheme 33: RRM approach to functionalized polycyclic systems.
  
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38. Scheme 34: Sequential RRM approach to functionalized tricyclic ring system 166.
  
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39. Scheme 35: RRM protocol to functionalized CDE tricyclic ring system of schintrilactones A and B.
  
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40. Scheme 36: Sequential RRM approach to 7/5 fused bicyclic systems.
  
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41. Scheme 37: Sequential ROM-RCM protocol for the synthesis of bicyclic sugar derivatives.
  
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42. Scheme 38: ROM–RCM sequence of the norbornene derivatives 186 and 187.
  
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43. Scheme 39: RRM approach toward highly functionalized bridge tricyclic system.
  
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44. Scheme 40: RRM approach toward highly functionalized tricyclic systems.
  
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45. Scheme 41: Synthesis of hexacyclic compound 203 by RRM approach.
  
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46. Scheme 42: RRM approach toward C₃-symmetric chiral trimethylsumanene 209.
  
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47. Scheme 43: Triquinane synthesis via IMDA reaction and RRM protocol.
  
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48. Scheme 44: RRM approach to polycyclic compounds.
  
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49. Scheme 45: RRM strategy toward cis-fused bicyclo[3.3.0]carbocycles.
  
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50. Scheme 46: RRM protocol towards the synthesis of bicyclic lactone 230.
  
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51. Scheme 47: RRM approach to spiro heterocyclic compounds.
  
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52. Scheme 48: RRM approach to spiro heterocyclic compounds.
  
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53. Scheme 49: RRM approach to regioselective pyrrolizidine system 240.
  
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54. Scheme 50: RRM approach to functionalized bicyclic derivatives.
  
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55. Scheme 51: RRM approach to tricyclic derivatives 249 and 250.
  
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56. Scheme 52: RRM approach to perhydroindoline derivative and spiro system.
  
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57. Scheme 53: RRM approach to bicyclic pyran derivatives.
  
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58. Scheme 54: RRM of various functionalized oxanorbornene systems.
  
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59. Scheme 55: RRM to assemble the spiro fused-furanone core unit. (i) 129, benzene, 55 °C, 3 days; (ii) Ph₃P=CH₂B...
  
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60. Scheme 56: RRM protocol to norbornenyl sultam systems.
  
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61. Scheme 57: Ugi-RRM protocol for the synthesis of 2-aza-7-oxabicyclo system.
  
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62. Scheme 58: Synthesis of spiroketal systems via RRM protocol.
  
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63. Scheme 59: RRM approach to cis-fused heterotricyclic system.
  
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64. Scheme 60: RRM protocol to functionalized bicyclic systems.
  
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65. Scheme 61: ROM/RCM/CM cascade to generate bicyclic scaffolds.
  
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66. Scheme 62: RCM of ROM/CM product.
  
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67. Scheme 63: RRM protocol to bicyclic isoxazolidine ring system.
  
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68. Scheme 64: RRM approach toward the total synthesis of (±)-8-epihalosaline (300).
  
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69. Scheme 65: Sequential RRM approach to decalin 304 and 7/6 fused 305 systems.
  
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70. Scheme 66: RRM protocol to various fused carbocyclic derivatives.
  
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71. Scheme 67: RRM to cis-hydrindenol derivatives.
  
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72. Scheme 68: RRM protocol towards the cis-hydrindenol derivatives.
  
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73. Scheme 69: RRM approach toward the synthesis of diversed polycyclic lactams.
  
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74. Scheme 70: RRM approach towards synthesis of hexacyclic compound 324.
  
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75. Scheme 71: RRM protocol to generate luciduline precursor 327 with catalyst 2.
  
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76. Scheme 72: RRM protocol to key building block 330.
  
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77. Scheme 73: RRM approach towards the synthesis of key intermediate 335.
  
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78. Scheme 74: RRM protocol to highly functionalized spiro-pyran system 339.
  
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79. Scheme 75: RRM to various bicyclic polyether derivatives.
  
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Graphical Abstract

Beilstein J. Org. Chem. 2015, 11, 1833–1864, doi:10.3762/bjoc.11.199

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Cross metathesis of unsaturated epoxides for the synthesis of polyfunctional building blocks

Meriem K. Abderrezak,
Kristýna Šichová,
Nancy Dominguez-Boblett,
Antoine Dupé,
Zahia Kabouche,
Christian Bruneau and
Cédric Fischmeister

Full Research Paper
Published 08 Oct 2015

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1. Graphical Abstract
2. Scheme 1: Cross metathesis of 1 with methyl acrylate.
  
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3. Scheme 2: Cross metathesis of 1 with acrylonitrile.
  
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4. Scheme 3: Tandem cross metathesis/hydrogenation.
  
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5. Scheme 4: Trifunctional compounds obtained by ring-opening of epoxide 4.
  
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Graphical Abstract

Beilstein J. Org. Chem. 2015, 11, 1876–1880, doi:10.3762/bjoc.11.201

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Profluorescent substrates for the screening of olefin metathesis catalysts

Raphael Reuter and
Thomas R. Ward

Full Research Paper
Published 12 Oct 2015

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1. Graphical Abstract
2. Figure 1: Catalysts 1–4 tested for the metathesis of profluorescent substrates.
  
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3. Scheme 1: Two profluorescent substrates yielding fluorescent products upon ring-closing metathesis.
  
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4. Scheme 2: Synthesis of the two profluorescent substrates amenable to ring-closing metathesis.
  
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5. Figure 2: Fluorescence evolution resulting from closing metathesis of umbelliferone precursor 8 (λ_excitation ...
  
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6. Figure 3: Fluorescence evolution resulting from closing metathesis of fluorescence–quencher substrate 5 (λ_exc...
  
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7. Figure 4: Comparison of kinetics measured by HPLC a) and by a plate reader b) for the ring-closing metathesis...
  
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Graphical Abstract

Beilstein J. Org. Chem. 2015, 11, 1886–1892, doi:10.3762/bjoc.11.203

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Stereochemistry of ring-opening/cross metathesis reactions of exo- and endo-7-oxabicyclo[2.2.1]hept-5-ene-2-carbonitriles with allyl alcohol and allyl acetate

Piotr Wałejko,
Michał Dąbrowski,
Lech Szczepaniak,
Jacek W. Morzycki and
Stanisław Witkowski

Full Research Paper
Published 13 Oct 2015

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1. Graphical Abstract
2. Scheme 1: ROCM reactions of 7-oxanorbornene.
  
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3. Figure 1: Chemical structures of catalysts [Ru]1–6 used in this work.
  
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4. Scheme 2: Metathesis products of exo- and endo-7-oxabicyclo[2.2.1]hept-5-en-2-carbonitriles (1 and 2) with al...
  
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5. Figure 2: Representative GC chromatograms recorded from crude reaction mixtures described in Table 1: a) entry 1 and...
  
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6. Scheme 3: The plausible mechanism of the formation of ROCM and ROMP products from exo- or endo-7-oxabicyclo[2...
  
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7. Figure 3: Numbering of carbon atoms in cross metathesis products.
  
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Graphical Abstract

Beilstein J. Org. Chem. 2015, 11, 1893–1901, doi:10.3762/bjoc.11.204

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New aryloxybenzylidene ruthenium chelates – synthesis, reactivity and catalytic performance in ROMP

Patrycja Żak,
Szymon Rogalski,
Mariusz Majchrzak,
Maciej Kubicki and
Cezary Pietraszuk

Full Research Paper
Published 14 Oct 2015

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1. Graphical Abstract
2. Figure 1: Coordination motif of latent catalyst of olefin metathesis in which alkylidene ligand is bound to t...
  
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3. Figure 2: Known latent catalysts of olefin metathesis in which alkylidene ligands are bound to a heteroatom, ...
  
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4. Figure 3: Selected, known aryloxybenzylidene chelates [9,10].
  
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5. Scheme 1: Synthesis of catalyst precursors 4–6 [11].
  
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6. Scheme 2: Synthesis of catalysts 8–10.
  
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7. Scheme 3: Synthesis of catalysts 13 and 14.
  
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8. Figure 4: ROMP of COD. Conditions: CH₂Cl₂, 40 °C, 0.5 M, [COD]:[Ru] = 20000; For clarity, only two representa...
  
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9. Figure 5: ROMP of cod. Conditions: CH₂Cl₂, 40 °C, 0.5 M, [cod]:[Ru] = 20000; For clarity only representative ...
  
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10. Scheme 4: ROMP of monomer 15.
  
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11. Figure 6: ROMP of monomer 15. Conditions: CDCl₃, 40 °C, 0.08 M, [15]:[Ru] = 200.
  
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12. Figure 7: ROMP of monomer 15. Conditions: CDCl₃, 23 °C, 0.08 M, [15]:[Ru] = 200.
  
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13. Scheme 5: Formation of phosphine free dimeric complex in the presence of CuCl.
  
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14. Figure 8: A perspective view of complex 16, the ellipsoids are drawn at the 50% probability level. Hydrogen a...
  
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15. Scheme 6: Synthesis of complexes 1a and 8 starting from dimer 16.
  
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16. Scheme 7: Activation of complex 8 with one equivalent of HCl.
  
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Graphical Abstract

Beilstein J. Org. Chem. 2015, 11, 1910–1916, doi:10.3762/bjoc.11.206

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Hexacoordinate Ru-based olefin metathesis catalysts with pH-responsive N-heterocyclic carbene (NHC) and N-donor ligands for ROMP reactions in non-aqueous, aqueous and emulsion conditions

Shawna L. Balof,
K. Owen Nix,
Matthew S. Olliff,
Sarah E. Roessler,
Arpita Saha,
Kevin B. Müller,
Ulrich Behrens,
Edward J. Valente and
Hans-Jörg Schanz

Full Research Paper
Published 21 Oct 2015

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1. Graphical Abstract
2. Figure 1: Hydrophilic and/or pH-responsive Ru–alkylidene complexes 1–7 for olefin metathesis.
  
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3. Scheme 1: Synthesis of 2^nd Grubbs-type generation complex 9.
  
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4. Scheme 2: Synthesis of hexacoordinate, pH-responsive complexes 11 and 12.
  
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5. Figure 2: ORTEP diagram for H₂ITap(DMAP)₂Cl₂Ru=CH-SPh (12). The positions of the hydrogen atoms were calculat...
  
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6. Scheme 3: ROMP reactions conducted under microemulsion conditions.
  
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7. Scheme 4: Proposed formation of catalytic species 14 and 15 under emulsion ROMP conditions.
  
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8. Figure 3: AFM image produced from COE/DCPD latex film. Measurement: AFM tapping at room temperature, material...
  
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Graphical Abstract

Beilstein J. Org. Chem. 2015, 11, 1960–1972, doi:10.3762/bjoc.11.212

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Olefin metathesis in air

Lorenzo Piola,
Fady Nahra and
Steven P. Nolan

Review
Published 30 Oct 2015

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1. Graphical Abstract
2. Scheme 1: Polymerization of 7-oxanorbornene in water.
  
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3. Scheme 2: Synthesis of the first well-defined ruthenium carbene.
  
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4. Scheme 3: Synthesis of Grubbs' 1^st generation catalyst.
  
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5. Figure 1: NHC-Ruthenium complexes and widely used NHC carbenes.
  
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6. Scheme 4: Access to 21 from the Grubbs’ 1^st generation catalyst and its one-pot synthesis.
  
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7. Scheme 5: Synthesis of supported Hoveyda-type catalyst.
  
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8. Figure 2: Scope of RCM reactions with supported Hoveyda-type catalyst. Reaction conditions: 24 (5 mol %), non...
  
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9. Scheme 6: Synthesis of 33 by Hoveyda and Blechert.
  
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10. Figure 3: Synthesis of chiral Hoveyda–Grubbs type catalyst and its use in RO/CM.
  
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11. Scheme 7: Synthesis of 41.
  
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12. Figure 4: RCM reactions in air using 41 as catalyst. Reaction conditions: 41 (5 mol %), MeOH (0.05 M), 22 °C,...
  
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13. Figure 5: CM-type reactions in air using 41 as catalyst. Reaction conditions: 41 (5 mol %), 22 °C, 12 h, in a...
  
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14. Figure 6: Grela's complex (54) and reaction scope in air. Reaction conditions: catalyst, substrate (0.25 mmol...
  
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15. Figure 7: Abell's complex (61) and its RCM reaction scope in air. Reaction condition: 10 mol % of 61, refluxi...
  
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16. Figure 8: Catalysts used by Meier in air.
  
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17. Figure 9: Ammonium chloride-tagged complexes.
  
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18. Figure 10: Scorpio-type complexes.
  
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19. Scheme 8: Synthesis of Grubbs' 3^rd generation catalyst.
  
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20. Figure 11: Indenylidene complexes.
  
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21. Figure 12: Commercially available complexes evaluated under air.
  
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22. Figure 13: Grela's N,N-unsymmetrically substituted complexes.
  
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23. Scheme 9: Synthesis of phosphite-based catalysts.
  
  Jump to Scheme 9
24. Figure 14: Catalysts used by the Cazin group.
  
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25. Figure 15: RCM scope in air with catalysts 33, 85 and 98a. Reaction conditions: Catalyst, substrate (0.25 mmol...
  
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26. Figure 16: Synthesis of Schiff base-ruthenium complexes.
  
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27. Scheme 10: Schiff base–ruthenium complexes synthesized by Verpoort.
  
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28. Scheme 11: Synthesis of mixed Schiff base–NHC complexes.
  
  Jump to Scheme 11
29. Figure 17: Veerport's indenylidene Schiff-base complexes.
  
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Graphical Abstract

Beilstein J. Org. Chem. 2015, 11, 2038–2056, doi:10.3762/bjoc.11.221

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Ru complexes of Hoveyda–Grubbs type immobilized on lamellar zeolites: activity in olefin metathesis reactions

Hynek Balcar,
Naděžda Žilková,
Martin Kubů,
Michal Mazur,
Zdeněk Bastl and
Jiří Čejka

Full Research Paper
Published 04 Nov 2015

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1. Graphical Abstract
2. Figure 1: Hoveyda–Grubbs type catalysts used for immobilization.
  
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3. Scheme 1: RCM of (−)-β-citronellene (1) and N,N-diallyl-2,2,2-trifluoroacetamide (2).
  
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4. Figure 2: Conversion vs time dependence for RCM of (−)-β-citronellene over HGIIN⁺Cl⁻/MCM-36 (●), HGIIN⁺Cl⁻/SB...
  
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5. Figure 3: Conversion vs. time dependences for RCM of DAF over catalysts HGIIN⁺Cl⁻/MCM-22 (▲), HGIIN⁺Cl⁻/MCM-5...
  
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6. Figure 4: Splitting test for HGIIN⁺Cl⁻/MCM-56 in RCM of (−)-β-citronellene. Toluene, 60 °C, molar ratio (−)-β...
  
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7. Figure 5: Self-metathesis of methyl oleate over HGIIN⁺Cl⁻/SBA-15 (■), HGIIN⁺Cl⁻/MCM-22 (▲), HGIIN⁺Cl⁻/MCM-56 ...
  
  Jump to Figure 5
8. Scheme 2: Cross-metathesis of methyl oleate with cis-3-hexenyl acetate.
  
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9. Figure 6: Conversion curves for CM of methyl oleate (full symbols) with cis-3-hexenyl acetate (open symbols) ...
  
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Graphical Abstract

Beilstein J. Org. Chem. 2015, 11, 2087–2096, doi:10.3762/bjoc.11.225

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Computational study of productive and non-productive cycles in fluoroalkene metathesis

Markéta Rybáčková,
Jan Hošek,
Ondřej Šimůnek,
Viola Kolaříková and
Jaroslav Kvíčala

Full Research Paper
Published 10 Nov 2015

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1. Graphical Abstract
2. Scheme 1: Initiation, productive and non-productive cycles in alkene homometathesis.
  
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3. Figure 1: Initiation phase of the reaction of HG2 with ethene (1) and 1,1-difluoroethene (2).
  
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4. Figure 2: Initiation phase of the reaction of HG2 with ethene (1) and 1-fluoroethene (3).
  
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5. Figure 3: First part A of the catalytic cycle of homometathesis of 1,1-difluoroethene (2).
  
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6. Figure 4: Computed structures of complexes s2j and a2j.
  
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7. Figure 5: Second part B of the catalytic cycle of homometathesis of 1,1-difluoroethene (2).
  
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8. Figure 6: First part A of the catalytic cycle of homometathesis of 1-fluoroethene (3).
  
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9. Figure 7: Second part B of the catalytic cycle of homometathesis of 1-fluoroethene (3).
  
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10. Figure 8: Non-productive catalytic cycle of homometathesis of tetrafluoroethene (4).
  
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11. Figure 9: First part A of the catalytic cycle of homometathesis of chlorotrifluoroethene (5).
  
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12. Figure 10: Second part B of the catalytic cycle of homometathesis of chlorotrifluoroethene (5).
  
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Graphical Abstract

Beilstein J. Org. Chem. 2015, 11, 2150–2157, doi:10.3762/bjoc.11.232

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Beyond catalyst deactivation: cross-metathesis involving olefins containing N-heteroaromatics

Kevin Lafaye,
Cyril Bosset,
Lionel Nicolas,
Amandine Guérinot and
Janine Cossy

Review
Published 18 Nov 2015

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1. Graphical Abstract
2. Figure 1: Some ruthenium catalysts for metathesis reactions.
  
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3. Scheme 1: Decomposition of methylidenes 1 and 2.
  
  Jump to Scheme 1
4. Scheme 2: Deactivation of G-HII in the presence of ethylene.
  
  Jump to Scheme 2
5. Scheme 3: Reaction between GI/GII and n-BuNH₂.
  
  Jump to Scheme 3
6. Scheme 4: Reaction of GII with amines a–d.
  
  Jump to Scheme 4
7. Scheme 5: Amine-induced decomposition of GII methylidene 2.
  
  Jump to Scheme 5
8. Scheme 6: Amine-induced decomposition of GII in RCM conditions.
  
  Jump to Scheme 6
9. Scheme 7: Deactivation of methylidene 2 in the presence of pyridine.
  
  Jump to Scheme 7
10. Scheme 8: Reaction of G-HII with various amines.
  
  Jump to Scheme 8
11. Scheme 9: Formation of olefin 22 from styrene.
  
  Jump to Scheme 9
12. Scheme 10: Hypothetic deactivation pathway of G-HII.
  
  Jump to Scheme 10
13. Scheme 11: RCM of dienic pyridinium salts.
  
  Jump to Scheme 11
14. Scheme 12: Synthesis of polycyclic scaffolds using RCM.
  
  Jump to Scheme 12
15. Scheme 13: Enyne ring-closing metathesis.
  
  Jump to Scheme 13
16. Scheme 14: Synthesis of (R)-(+)-muscopyridine using a RCM strategy.
  
  Jump to Scheme 14
17. Scheme 15: Synthesis of a tris-pyrrole macrocycle.
  
  Jump to Scheme 15
18. Scheme 16: Synthesis of a bicyclic imidazole.
  
  Jump to Scheme 16
19. Scheme 17: RCM using Schrock’s catalyst 44.
  
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20. Scheme 18: Synthesis of 1,6-pyrido-diazocine 46 by using a RCM.
  
  Jump to Scheme 18
21. Scheme 19: Synthesis of fused pyrimido-azepines through RCM.
  
  Jump to Scheme 19
22. Scheme 20: RCM involving alkenes containing various N-heteroaromatics.
  
  Jump to Scheme 20
23. Scheme 21: Synthesis of dihydroisoquinoline using a RCM.
  
  Jump to Scheme 21
24. Scheme 22: Formation of tricyclic compound 59.
  
  Jump to Scheme 22
25. Scheme 23: RCM in the synthesis of normuscopyridine.
  
  Jump to Scheme 23
26. Scheme 24: Synthesis of macrocycle 64.
  
  Jump to Scheme 24
27. Scheme 25: Synthesis of macrocycles possessing an imidazole group.
  
  Jump to Scheme 25
28. Scheme 26: Retrosynthesis of an analogue of erythromycin.
  
  Jump to Scheme 26
29. Scheme 27: Retrosynthesis of haminol A.
  
  Jump to Scheme 27
30. Scheme 28: CM involving 3-vinylpyridine 70 with 71 and vinylpyridine 70 with 73.
  
  Jump to Scheme 28
31. Scheme 29: Revised retrosynthesis of haminol A.
  
  Jump to Scheme 29
32. Scheme 30: CM between 78 and crotonaldehyde.
  
  Jump to Scheme 30
33. Scheme 31: Hypothesized deactivation pathway.
  
  Jump to Scheme 31
34. Scheme 32: CM involving an allyl sulfide containing a quinoline.
  
  Jump to Scheme 32
35. Scheme 33: CM involving allylic sulfide possessing a quinoxaline or a phenanthroline.
  
  Jump to Scheme 33
36. Scheme 34: CM between an acrylate and a 2-methoxy-5-bromo pyridine.
  
  Jump to Scheme 34
37. Scheme 35: Successful CM of an alkene containing a 2-chloropyridine.
  
  Jump to Scheme 35
38. Scheme 36: Variation of the substituent on the pyridine ring.
  
  Jump to Scheme 36
39. Scheme 37: CM involving alkenes containing a variety of N-heteroaromatics.
  
  Jump to Scheme 37

Graphical Abstract

Beilstein J. Org. Chem. 2015, 11, 2223–2241, doi:10.3762/bjoc.11.241

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Recent advances in metathesis-derived polymers containing transition metals in the side chain

Ileana Dragutan,
Valerian Dragutan,
Bogdan C. Simionescu,
Albert Demonceau and
Helmut Fischer

Review
Published 28 Dec 2015

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Album
1. Graphical Abstract
2. Scheme 1: Synthesis of homopolymers containing ferrocenyl and tetraethylene glycol groups.
  
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3. Scheme 2: Synthesis of redox-robust triazolylbiferrocenyl polymers 4.
  
  Jump to Scheme 2
4. Scheme 3: Synthesis of cobaltocenium-containing polymers by ROMP.
  
  Jump to Scheme 3
5. Scheme 4: Cobaltocenium-appending copolymers by the ROMP approach (X = PF₆, Y = BPh₄ or Cl).
  
  Jump to Scheme 4
6. Scheme 5: Cobalt-containing polymers by click and ROMP approach.
  
  Jump to Scheme 5
7. Scheme 6: Synthesis of new cobalt-integrating block copolymers.
  
  Jump to Scheme 6
8. Scheme 7: Two alternative routes for the synthesis of redox-active cobalticenium-tethered polyelectrolytes.
  
  Jump to Scheme 7
9. Scheme 8: Oxanorbornene monomers for the synthesis of Ru-containing polymers by ROMP.
  
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10. Scheme 9: ROMP synthesis of Ru-containing homopolymers.
  
  Jump to Scheme 9
11. Scheme 10: Synthesis of diblock copolymers incorporating ruthenium.
  
  Jump to Scheme 10
12. Scheme 11: Synthesis of Ru triblock copolymers.
  
  Jump to Scheme 11
13. Scheme 12: Synthesis of cross-linked Ru-containing triblock copolymers.
  
  Jump to Scheme 12
14. Scheme 13: Synthesis of Ir-containing homopolymers by ROMP.
  
  Jump to Scheme 13
15. Scheme 14: Monomers for Ir- and Os-containing ROMP polymers.
  
  Jump to Scheme 14
16. Scheme 15: ROMP block copolymers integrating Ir in their side chains.
  
  Jump to Scheme 15
17. Scheme 16: Synthesis of Rh-containing block copolymers.
  
  Jump to Scheme 16
18. Scheme 17: Access to rhodocenium-containing metallopolymers by ROMP.
  
  Jump to Scheme 17
19. Scheme 18: Synthesis of homopolymers equipped with Cu coordination centers.
  
  Jump to Scheme 18
20. Scheme 19: Synthesis of Cu-containing copolymers (spacer = –(CH₂)₅–; >C=O).
  
  Jump to Scheme 19
21. Scheme 20: Synthesis of polynorbornene bearing a polyoxometalate (POM) cluster in the side chain.
  
  Jump to Scheme 20
22. Scheme 21: Synthesis of Eu-containing copolymers by a ROMP-based route.
  
  Jump to Scheme 21

Graphical Abstract

Beilstein J. Org. Chem. 2015, 11, 2747–2762, doi:10.3762/bjoc.11.296

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