Structural requirements in chiral diphosphine-rhodium complexes: III. Small scale method for fresh preparation of cationic diop-rhodium complexes and comparison with neutral diop-rhodium complexes

doi:10.1016/S0022-328X(00)87118-1

Journal of Organometallic Chemistry

Volume 112, Issue 3, 8 June 1976, Pages 355-360

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Abstract

(—)-2,3-Isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane (DIOP) was used in cationic rhodium(I)-diphosphine complexes, freshly prepared on a milligram scale, to catalyze the asymmetric hydrogenation of (Z)-α-acetamidocinnamic acid. These cationic complexes were found not to be air stable over a period of time, but when utilized after storage under argon reproducible kinetic results were noted, and the optical purity of the reduction product was found to be independent of the age of the cationic complex. The cationic rhodium(I)DIOP complex was found to be a more reactive complex than the corresponding neutral chlororhodium(I)-DIOP complex when used in asymmetric hydrogenations, but both gave the same optical yield.

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Optically active transition metal complexes. Part 119: New rhodium(I) complexes containing two different types of optically active ligands
1998, Tetrahedron Asymmetry
The synthesis of novel rhodium(I) complexes containing two different chiral ligands is described. These ligands are on the one hand (−)-diop and on the other hand various optically active pyrroleimines, which derive from 1-phenylethylamine or 1-cyclohexylethylamine with an (R)- or (S)-configuration. The resulting (−)-diop–pyrrolylimine–rhodium(I) complexes are diastereomers and are expected to give different stereoselectivities in enantioselective catalysis (double stereoselection). In addition, the synthesis of novel rhodium(I) complexes containing 1,5-cyclooctadiene and various chiral pyrroleoxazoline ligands is described. All the complexes are used in the enantioselective hydrogenation of ketopantolactone (see following paper).
Chirale Bisphosphane VIII. Die enantioselektive Hydrierung von α-Acetamidozimtsäure durch kationische Rhodium(I)-Komplexe mit optisch reinen (1S,2S)-Cyclopentan-1,2-diyl-bis(phosphonigsäurediester)- und (1S,2S)-Cyclopentan-1,2-diyl-bis(phosphonigsäurediamid)-Liganden<sup>1</sup>
1998, Journal of Organometallic Chemistry
Treatment of [(1,5-COD)₂Rh]O₃SCF₃ with optically active P₂ ligands of the type (1S,2S)-C₅H₈(PR₂)₂ [PR₂=P(OMe)₂ (3), P(OPh)₂ (4), P[OCH(Me)Et-(S)]₂ (5), P[2-OC₁₀H₆C₁₀H₆O-2′-(R)] (6), P(NC₄H₈O-cyclo)₂ (7)] gave cationic rhodium complexes bearing these new ligands, [(1,5-COD)Rh{(PR₂)₂C₅H₈-(1S,2S)}]O₃SCF₃ (Rh-3–7). Use of these as catalysts in the homogeneous enantioselective hydrogenation of α-acetamidocinnamic acid to N-acetylphenylalanine provided optical yields of 75–78% ee for the complexes [(1,5-COD)Rh{[P(OPh)₂]₂C₅H₈-(1S,2S)}]O₃SCF₃ (Rh-4) and [(1,5-COD)Rh{(P[OCH(Me)Et-(S)]₂)₂C₅H₈-(1S,2S)}]O₃SCF₃ (Rh-5), respectively.
Die Umsetzung von [(1,5-COD)₂Rh]O₃SCF₃ mit optisch aktiven P₂-Liganden des Typs (1S,2S)-C₅H₈(PR₂)₂ [PR₂=P(OMe)₂ (3), P(OPh)₂ (4), P[OCH(Me)Et-(S)]₂ (5), P[2-OC₁₀H₆C₁₀H₆O-2′-(R)] (6), P(NC₄H₈O-cyclo)₂ (7)] führte zu kationischen Rhodiumkomplexen dieser neuen Liganden, [(1,5-COD)Rh{(PR₂)₂C₅H₈-(1S,2S)}]O₃SCF₃ (Rh-3–7). Bei deren Einsatz als Katalysatoren der homogenen enantioselektiven Hydrierung von α-Acetamidozimtsäure zu N-Acetylphenylalanin wurden optische Ausbeuten von 75–78% ee für die Komplexe [(1,5-COD)Rh{[P(OPh)₂]₂C₅H₈-(1S,2S)}]O₃SCF₃ (Rh-4) and [(1,5-COD)Rh{(P[OCH(Me)Et-(S)]₂)₂C₅H₈-(1S,2S)}]O₃SCF₃ (Rh-5) erreicht.
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Homogeneous hydrogenation of substituted (Z)-ene-1,2-di-(−)-(1R, 3R, 4S)-methylcarbamate catalysed by rhodium complexes containing (+)-(2S,3S) or (−)-(2R,3R)-isopropylidene-2,3-dihydroxy-1,4-bis(diphenylphosphino)butane (DIOP) gives rise to the saturated products with a diastereomeric excess (de) of 47% and 40%, respectively. Hydrogenation of substituted (Z)-ene-1,2-di-iso-butylcarbamate affords an enantiomeric excess (ee) of 20% and 18%.
Homogeneous deuteriation of alkenes using [RhCl(4R,5R-DIOP)] catalysts
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Mass spectrometric analyses of the products from the homogeneous deuteriation of alkenes using the [RhCl(4R,5R-DIOP)] catalyst have shown that considerable quantities of polydeuteriated products are obtained. These products arise from the decomposition of the intermediate rhodium(III) alkyl complex [RhDCl(alkyl)(DIOP)] before the second atom of deuterium can be transferred to the alkyl ligand. Its decomposition by β-hydride abstraction brings about both polydeuteriation and scrambled addition of deuterium to the alkene. The yields of specifically deuteriated products are inferior to those obtained from Wilkinson-type catalysts. The best yields of dideuteroproducts are obtained from substituted alkenes that chelate to the catalyst and thereby stabilize the intermediate alkyl.
Catalytic asymmetric hydrogenation with rhodium complexes of improved DIOPS bearing para-dimethylamino group on the basis of our designing concept
1988, Tetrahedron Letters

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: For parts I-II see ref. 1

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Structural requirements in chiral diphosphine-rhodium complexes: III. Small scale method for fresh preparation of cationic diop-rhodium complexes and comparison with neutral diop-rhodium complexes

Abstract

Tetrahedron Lett.

J. Organometal. Chem.

J. Amer. Chem. Soc.

J. Amer. Chem. Soc.

Chem. Commun.

Ger. Offen. No. 2,123,063

J. Chem. Commun.

Ger. Offen. No. 2,210,968

Chem. Tech.

Ann. N.Y. Acad. Sci.

Adv. Chem. Ser., No. 132

J. Chem. Soc. Chem. Commun.