Contemporary organosilicon chemistry

Steve Marsden

Editorial
Published 08 Feb 2007

Beilstein J. Org. Chem. 2007, 3, No. 4, doi:10.1186/1860-5397-3-4

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Reaction of benzoxasilocines with aromatic aldehydes: Synthesis of homopterocarpans

Míriam Álvarez-Corral,
Cristóbal López-Sánchez,
Leticia Jiménez-González,
Antonio Rosales,
Manuel Muñoz-Dorado and
Ignacio Rodríguez-García

Full Research Paper
Published 08 Feb 2007

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1. Graphical Abstract
2. Scheme 1: Retrosynthetic analysis for the homopterocarpan skeleton.
  
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3. Scheme 2: Reagents: i CH₂ = CHCH₂SiMe₂Cl, Et₃N, DCM, 85%; ii 2^nd generation Grubbs catalyst, DCM, 91%.
  
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4. Scheme 3: Reagents: i: BF₃·Et₂O (1 eq), MeOH 95%; ii: substituted benzaldehydes, BF₃·Et₂O (1 eq), DCM; iii: s...
  
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5. Scheme 4: Reagents: i: a) OsO₄, KIO₄, THF-H₂O, 79%; b) LiAlH₄, Et₂, 0°C, 76%; iii: PPh₃, DIAD, THF, 70%.
  
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Beilstein J. Org. Chem. 2007, 3, No. 5, doi:10.1186/1860-5397-3-5

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Tether- directed synthesis of highly substituted oxasilacycles via an intramolecular allylation employing allylsilanes

Peter J. Jervis and
Liam R. Cox

Full Research Paper
Published 08 Feb 2007

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1. Graphical Abstract
2. Scheme 1: Synthesis using a Temporary Connection Strategy.
  
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3. Scheme 2: Intramolecular allylation of aldehyde 1 generates two out of the four possible oxasilacycles. The b...
  
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4. Scheme 3: The effect of introducing a methyl group α- to the aldehyde in the cyclisation precursor will depen...
  
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5. Scheme 4: Retrosynthesis of aldehyde anti-4.
  
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6. Scheme 5: Attempts to reduce the bulky aryl ester resulted in Si-O bond cleavage and over-reduction to the pr...
  
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7. Scheme 6: Preparation of syn- and anti-β-hydroxy esters.
  
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8. Scheme 7: Preparation of the syn- and anti-aldehyde cyclisation precursors 4.
  
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9. Scheme 8: Intramolecular allylation results.
  
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10. Figure 1: nOe data for the two oxasilacycles obtained from allylation of aldehyde anti-4b.
  
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Beilstein J. Org. Chem. 2007, 3, No. 6, doi:10.1186/1860-5397-3-6

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Generation of pyridyl coordinated organosilicon cation pool by oxidative Si-Si bond dissociation

Toshiki Nokami,
Ryoji Soma,
Yoshimasa Yamamoto,
Toshiyuki Kamei,
Kenichiro Itami and
Jun-ichi Yoshida

Preliminary Communication
Published 08 Feb 2007

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1. Graphical Abstract
2. Scheme 1: Electrochemical generation of carbocations by oxidative C-C bond dissociation.
  
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3. Scheme 2: Electrochemical generation and accumulation of organosilicon cation by oxidative Si-Si bond dissoci...
  
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4. Figure 1: Oxidation potentials (E_d; decomposition potential) of disilanes determined by rotating disk electro...
  
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5. Figure 2: Optimized structures of radical cations of 1,2-diphenyldisilane and 1,2-bis [o-(2-pyridyl)- phenyl]...
  
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6. Scheme 3: Electrochemical generation of organosilicon cation 3d.
  
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7. Figure 3: CSI-MS of organosilicon cation 3d at 0°C.
  
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8. Figure 4: Optimized structures of organosilicon cation 3d and silyl radical 4d by DFT calculations (B3LYP/LAN...
  
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9. Scheme 4: Reaction of organosilicon cation 3d with p-tolylmagnesium bromide.
  
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Beilstein J. Org. Chem. 2007, 3, No. 7, doi:10.1186/1860-5397-3-7

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Pd-catalysed [3 + 3] annelations in the stereoselective synthesis of indolizidines

Olivier Y. Provoost,
Andrew J. Hazelwood and
Joseph P. A. Harrity

Preliminary Communication
Published 08 Feb 2007

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1. Graphical Abstract
2. Scheme 1: [3 + 3] Annelation approach to indolizidine skeleta.
  
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3. Scheme 2: Enantiospecific aziridine synthesis (ADDP: 1,1'-(azodicarbonyl)dipiperidine).
  
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4. Scheme 3: Diastereoselective aldol addition.
  
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5. Scheme 4: Indolizidinone formation.
  
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6. Scheme 5: Preparation of a functionalised indolizidine.
  
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Beilstein J. Org. Chem. 2007, 3, No. 8, doi:10.1186/1860-5397-3-8

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Conformational rigidity of silicon- stereogenic silanes in asymmetric catalysis: A comparative study

Sebastian Rendler and
Martin Oestreich

Full Research Paper
Published 08 Feb 2007

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1. Graphical Abstract
2. Figure 1: Cyclic and acyclic sterically encumbered silanes.
  
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3. Scheme 1: Cyclic and acyclic chiral silanes as potent reagents for the silicon-to-carbon chirality transfer.
  
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4. Scheme 2: Kinetic resolution of secondary alcohols using a dehydrogenative coupling reaction.
  
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5. Scheme 3: Catalytic cycle for hydrosilylation.
  
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6. Scheme 4: Postulated catalytic cycle for dehydrogenative coupling.
  
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Beilstein J. Org. Chem. 2007, 3, No. 9, doi:10.1186/1860-5397-3-9

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Allylsilanes in the synthesis of three to seven membered rings: the silylcuprate strategy

Asunción Barbero,
Francisco J. Pulido and
M. Carmen Sañudo

Review
Published 22 May 2007

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1. Graphical Abstract
2. Scheme 1: The silylcupration of allenes.
  
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3. Scheme 2: Silylcupration of 1,2-propadiene and reaction with oxo compounds.
  
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4. Scheme 3: Silicon assisted cyclization of oxoallylsilanes.
  
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5. Scheme 4: Silylcupration of terminal alkynes bearing electron-withdrawing functions.
  
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6. Scheme 5: The acid-catalyzed cyclization of epoxyallylsilanes.
  
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7. Scheme 6: Intramolecular cyclization of TMS-epoxyallylsilanes.
  
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8. Scheme 7: Spiro-cyclopropanation from oxoallylsilanes.
  
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9. Scheme 8: Cyclobutane formation from hydroxy-functionalized allysilanes.
  
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10. Scheme 9: Cyclobutene formation from vinyltin cuprates and epoxides.
  
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11. Scheme 10: Silylcupration of 1,2-propadiene and reaction with α,β-unsaturated nitriles.
  
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12. Scheme 11: Cycloheptane formation from silylcupration of α,β-unsaturated imines.
  
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13. Scheme 12: Seven membered ring formation from functionalized allylsilanes.
  
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Beilstein J. Org. Chem. 2007, 3, No. 16, doi:10.1186/1860-5397-3-16

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The use of silicon- based tethers for the Pauson- Khand reaction

Adrian P. Dobbs,
Ian J. Miller and
Saša Martinović

Preliminary Communication
Published 06 Jul 2007

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1. Graphical Abstract
2. Scheme 1: Saigo's cycloisomerisation reaction under Pauson-Khand conditions.
  
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3. Scheme 2: Pauson-Khand reaction and tether-cleavage in wet acetonitrile.
  
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4. Scheme 3: Silyl-tethered allenic Pauson-Khand reaction reported by Brummond.
  
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5. Scheme 4: Intramolecular Pauson-Khand reaction of allyldimethyl- and allyldiphenylsilyl propargyl ethers repo...
  
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6. Scheme 5: Synthesis and attempted Pauson-Khand reactions of vinyldimethylsilyl- and vinyldiphenylsilyl ethers....
  
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7. Figure 1: Functionalised acetylenes prepared and used in silyl ether-tethered Pauson-Khand reactions. Yields ...
  
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8. Figure 2: Chain-functionalised acetylenes prepared and used in silyl ether-tethered Pauson-Khand reactions. Y...
  
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9. Figure 3: Possible structure of THF-oxidation/insertion product.
  
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10. Scheme 6: Model Pauson-Khand reaction of allyltrimethylsilane.
  
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11. Scheme 7: Preparation of allyldiisopropylsilyl ethers.
  
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12. Scheme 8: Pauson-Khand reaction of allyldiisopropylsilyl ethers.
  
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13. Scheme 9: Preparation of allyldiisopropylsilanes.
  
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14. Scheme 10: Attempted Mitsunobu reactions of diisopropylsilanols.
  
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15. Scheme 11: Preparation of alkynic diisopropylsilanes.
  
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16. Scheme 12: Preparation of allyldiisopropylsilyl ethers.
  
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17. Scheme 13: Preparation of acetals from dichlorodiphenylsilane.
  
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18. Scheme 14: Attempted Pauson-Khand reaction of allylpropargyldiphenylsilyl acetal.
  
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19. Scheme 15: Proposed diisopropylsilyl acetal formation.
  
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20. Scheme 16: Attempted allylpropargyldiisopropylsilyl acetal formation.
  
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21. Scheme 17: Attempted allylpropargyldiisopropylsilyl acetal formation.
  
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22. Scheme 18: Preparation of silicon-tethered Pauson-Khand precursors.
  
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23. Scheme 19: Failed Pauson-Khand reaction of a silicon-tethered substrate.
  
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Beilstein J. Org. Chem. 2007, 3, No. 21, doi:10.1186/1860-5397-3-21

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Single and double stereoselective fluorination of (E)-allylsilanes

Marcin Sawicki,
Angela Kwok,
Matthew Tredwell and
Véronique Gouverneur

Preliminary Communication
Published 25 Oct 2007

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1. Graphical Abstract
2. Scheme 1: Fluorination of branched allylsilanes A and B
  
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3. Scheme 2: Fluorination of anti (E)-1e
  
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4. Scheme 3: Double electrophilic fluorination of (E)-4
  
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5. Scheme 4: Conversion of 3 into diol 7
  
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Beilstein J. Org. Chem. 2007, 3, No. 34, doi:10.1186/1860-5397-3-34

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Contemporary organosilicon chemistry

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