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Schenk WA, Frisch J, Dürr M, et al. Oxidation of Thioether Ligands in Pseudotetrahedral Cyclopentadienylruthenium Complexes: Toward a New Stereoselective Synthesis of Chiral Sulfoxides(1). Inorg Chem. 1997;36(11):2372-2378doi: 10.1021/ic961280f.
Schenk, W. A., Frisch, J., Dürr, M., Burzlaff, N., Stalke, D., Fleischer, R., Adam, W., Prechtl, F., & Smerz, A. K. (1997). Oxidation of Thioether Ligands in Pseudotetrahedral Cyclopentadienylruthenium Complexes: Toward a New Stereoselective Synthesis of Chiral Sulfoxides(1). Inorganic chemistry, 36(11), 2372-2378. https://doi.org/10.1021/ic961280f
Schenk, Wolfdieter A., et al. "Oxidation of Thioether Ligands in Pseudotetrahedral Cyclopentadienylruthenium Complexes: Toward a New Stereoselective Synthesis of Chiral Sulfoxides(1)." Inorganic chemistry vol. 36,11 (1997): 2372-2378. doi: https://doi.org/10.1021/ic961280f
Schenk WA, Frisch J, Dürr M, Burzlaff N, Stalke D, Fleischer R, Adam W, Prechtl F, Smerz AK. Oxidation of Thioether Ligands in Pseudotetrahedral Cyclopentadienylruthenium Complexes: Toward a New Stereoselective Synthesis of Chiral Sulfoxides(1). Inorg Chem. 1997 May 21;36(11):2372-2378. doi: 10.1021/ic961280f. PMID: 11669873.
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Inorg Chem. 1997 May 21;36(11):2372-2378. doi: 10.1021/ic961280f.

Oxidation of Thioether Ligands in Pseudotetrahedral Cyclopentadienylruthenium Complexes: Toward a New Stereoselective Synthesis of Chiral Sulfoxides(1).

Inorganic chemistry

Wolfdieter A. Schenk, Jürgen Frisch, Michael Dürr, Nicolai Burzlaff, Dietmar Stalke, Roland Fleischer, Waldemar Adam, Frank Prechtl, Alexander K. Smerz

Affiliations

  1. Institut für Anorganische Chemie and Institut für Organische Chemie, University of Würzburg, Am Hubland, D-97074 Würzburg, Germany.

PMID: 11669873 DOI: 10.1021/ic961280f

Abstract

Ionic ruthenium thioether complexes [Cp(LL')Ru(SRR')]PF(6) (LL' = Ph(2)PCH(2)PPh(2) (1), Ph(2)PC(2)H(4)PPh(2) (2), (Ph(3)P, CO) (3), Me(2)PC(2)H(4)PPh(2) (4), (S,S)-Ph(2)PCHMeCHMePPh(2) (5), SRR' = MeSPh (a), MeS-i-Pr (b), MeSBz (c), i-PrSBz (d), EtSBz (e), MeSCy (f), SC(4)H(8) (g)) were synthesized from the corresponding chloro complexes [Cp(LL')RuCl] and thioethers. 5a crystallized in the orthorhombic system, space group P2(1)2(1)2(1) (No. 19), with a = 11.269(3) Å, b = 15.104(2) Å, c = 23.177(4) Å, and Z = 4. 5b crystallized in the monoclinic system, space group P2(1) (No. 4), with a = 10.539(5) Å, b = 16.216(9) Å, c = 11.011(8) Å, beta = 106.04(2) degrees, and Z = 2. A similar ligand exchange reaction yielded the analogous sulfoxide complexes [Cp(LL')Ru(S(O)RR')]PF(6) (6-10). 10a crystallized in the orthorhombic system, space group P2(1)2(1)2(1) (No. 19), with a = 14.1664(13) Å, b = 15.792(2) Å, c = 17.641(2) Å, and Z = 4. 10b.0.93CH(2)Cl(2) crystallized in the orthorhombic system, space group P2(1)2(1)2(1) (No. 19), with a = 12.069(2) Å, b = 17.379(2) Å, c = 19.760(5) Å, and Z = 4. The thioether complexes can also be directly converted to sulfoxide complexes with the strong oxygen transfer reagent dimethyldioxirane (DMD). No crossover products are formed when mixtures of two thioether complexes (e.g., 1a/2c or 1c/2a) are treated with DMD, demonstrating that no Ru-S bond cleavage is involved. Moderate diastereoselectivities are observed for the oxygen transfer to chiral, racemic thioether complexes 3 (8-28%) and 4 (34-60%). Oxidation of the (S,S)-CHIRAPHOS complexes 5, however, is highly stereoselective (de = 46-98%). Treatment of the sulfoxide complexes 10 with sodium iodide removes the chiral, nonracemic sulfoxides from the metal with retention of the configuration at sulfur.

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