Optical Activity from Asymmetric Transition Metal Atoms

Brunner, Henri

doi:10.1002/anie.197102491

Cited by 57 publications

(9 citation statements)

References 67 publications

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“…The optical rotations of the two enantiomers have opposite signs and, within the limits of error, the same magnitude. [18,19,24] The addition of mentholate ions to form diastereomers which only differ in the metal configuration is confined to cationic carbonyl complexes. Whereas the cationic manganese complexes in Scheme 1 are enantiomers, the cation in the complex [(h 5 -C 5 H 5 )Fe(CO) 2 PPh 3 ]PF 6 (3) [25] is prochiral.…”

Section: The First Optically Active Transition Metal Compounds With Fmentioning

confidence: 99%

Optically Active Organometallic Compounds of Transition Elements with Chiral Metal Atoms

Brunner¹

1999

Angew. Chem. Int. Ed.

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326

144

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Chiral transition metal atoms are not only present in tris-chelate complexes [M(LL) ] , which were already resolved into the enantiomers by Alfred Werner, but also in organometallic half-sandwich complexes such as 1 with three- or four-legged piano-stool structure. These complexes have been tools in the elucidation of the spatial course of reactions and in organic syntheses. Applications in enantioselective catalysis are beginning to show up.

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Section: The First Optically Active Transition Metal Compounds With Fmentioning

confidence: 99%

Optically Active Organometallic Compounds of Transition Elements with Chiral Metal Atoms

Brunner¹

1999

Angew. Chem. Int. Ed.

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326

144

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“…A caveat is presented regarding the possibility that chiral ligand conformations may be involved rather than epimeric chiral metal centers.Chiral transition metal organometallics were first resolved more than a quarter of a century ago. [1][2][3][4][5][6] A large class of these complexes are piano-stool type structures containing an Z 6arene or Z 5 -cyclopentadienyl ligand, such…”

mentioning

confidence: 99%

“…Chiral transition metal organometallics were first resolved more than a quarter of a century ago. [1][2][3][4][5][6] A large class of these complexes are piano-stool type structures containing an Z 6arene or Z 5 -cyclopentadienyl ligand, such…”

mentioning

confidence: 99%

Nonrigid diastereomers: epimerization at chiral metal centers or chiral ligand conformations?

2003

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“…In these systems, one ligand is generally a cyclopentadienyl (Cp) or an arene derivative and their geometry is better defined as piano‐stool rather than tetrahedral. The higher stability of these complexes with regard to pure tetrahedral iron complexes derives from an additional stabilization ensured by a π back‐bonding from the iron atom to the empty antibonding orbitals of the cyclopentadienyl ligand [8c] . As a consequence several half‐sandwich chiral complexes were described as effective stereoselective catalysts, especially in C−C bond forming reactions.…”

Section: Tetrahedral Chiral Iron Complexes With Four Ligandsmentioning

confidence: 99%

Chiral Iron Complexes in Asymmetric Organic Transformations

2021

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Transition metal chiral catalysts can feature metal stereocenters in different coordination geometries. In the case of iron, both octahedral and tetrahedral geometries possessing a chirotopic iron atom have been synthesized and tested in stereoselective organic transformations. The configurational stability of these complexes, which in some cases is hampered by decomplexation and recomplexation of labile ligands, is achieved by the use of multidentate ligands in octahedral complexes, and of cyclopentadienyl anions (half sandwich complexes) in the case of tetrahedral structures. The use of octahedral iron complexes featuring configurationally stable iron stereocenters is reviewed in highly enantioselective reductions (hydrogenation and transfer hydrogenation of ketones) and oxidations (cis‐dihydroxylation of alkenes, epoxidation, sulfoxidation), while the use tetradentate iron complexes is described in C−C bond‐forming reactions and reductions.

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Optical Activity from Asymmetric Transition Metal Atoms

Cited by 57 publications

References 67 publications

Optically Active Organometallic Compounds of Transition Elements with Chiral Metal Atoms

Optically Active Organometallic Compounds of Transition Elements with Chiral Metal Atoms

Nonrigid diastereomers: epimerization at chiral metal centers or chiral ligand conformations?

Chiral Iron Complexes in Asymmetric Organic Transformations

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