Enantioselective organic syntheses using chiral transition metal complexes V. (2S,3S)-Bis(dibenzophospholyl)butane, a rigid (S,S)-CHIRAPHOS analog |
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Authors: | Wolfdieter A Schenk Michael Stubbe and Michael Hagel |
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Institution: | Institut für Anorganische Chemie der Universität Würzburg, Am Hubland, D-97074 Würzburg, Germany |
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Abstract: | The P–Ph cleavage of phenyldibenzophosphole (1) with lithium in THF gives lithium dibenzophospholide (2). Reaction of 2 with ethyleneglycol ditosylate produces the known chelate ligand 1,2-bis(dibenzophospholyl)ethane (3) in good yield. Similarly, 2 and (2R,3R)-butanediol ditosylate give the new chiral chelate ligand (2S,3S)-bis(dibenzophospholyl)butane (4). Ligand exchange of CpRu(PPh3)2Cl] with 3 or 4 yields the halfsandwich complexes CpRu(C12H8PC2H4PC12H8)Cl] (5) and CpRu((S,S)-C12H8PCHMeCHMePC12H8)Cl] (6). Complex 6 was characterized crystallographically (monoclinic, space group P21 (no. 4), a=820.6(4), b=1501.0(3), c=1172.8(6) pm, β=108.87(2)°, V=1.367(1)×109 pm3, Z=2). The most conspicuous feature of the structure of 6 is the perfect coplanarity of the two dibenzophosphole moieties imposed by their steric interaction with the Cp ligand. Complex 6 and the thiophene complex CpRu((S,S)-C12H8PCHMeCHMePC12H8)(SC4H4)]BF4 (7) derived therefrom are remarkably unreactive with regard to ligand substitutions. A possible explanation is the lack of intramolecular –C stabilization en route to the transition state of ligand substitution. The enantiomeric purity of 6 and 7 could nevertheless be demonstrated by conversion to diastereomerically pure CpRu((S,S)-C12H8PCHMeCHMePC12H8)((S)-CNCHMePh)]BF4 (8). |
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Keywords: | Chiral auxiliaries Phosphine ligands Phospholes Ruthenium |
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