Optically active transition-metal complexes. 85. The BF3-promoted carbonylation of CpFe(CO)(L)Me compounds - a reaction stereospecific at low temperatures

Brunner, Henri; Hammer, Benedikt; Bernal, Ivan; Draux, Madeleine

doi:10.1021/om50005a019

Cited by 42 publications

(14 citation statements)

References 5 publications

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“…The molecule of 2 (Figure 1) has the classic “piano stool” structure as, for example, in [FeCp(COCH 3 )(CO)(PPh 3 )] 18. The Fe1−C8 distance [2.042(3) Å] is typical for an iron‐carbon σ‐bond and of similar length as in [Co(CH 2 N ‐phthaloyl)(CO) 4 ] from Marko and co‐workers15 and in [FeCp(CH 3 )(CO){Ph 2 PN(CH 3 )CH(CH 3 )Ph} 19. In the crystal, the Cp rings of different molecules of 1 are arranged in a parallel fashion.…”

Section: Phthalimidomethyl and ‐Acetyl Complexes Of Iron And Rhenium mentioning

confidence: 95%

Aminomethyl and Aminoacetyl Complexes of Palladium(II), Platinum(II), Iron(II) and Rhenium(I) with N‐Phthaloyl as Amino Protecting Group and Mechanistic Studies on the Palladium‐Catalyzed Amidocarbonylation

et al. 2004

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New aminomethyl and aminoacetyl complexes with N‐phthaloyl as the amino protecting group were synthesised by oxidative addition of N‐phthaloylmethyl or ‐acetyl halide to carbonylmetallates or to Pd(PPh3)4 or [Pt(C2H4)(PPh3)2] to give [Re{C(O)CH2N‐phthaloyl}(CO)5] (1), [FeCp(CH2N‐phthaloyl)(CO)2] (2), [FeCp{C(O)CH2N‐phthaloyl}(CO)2] (3), trans‐[PdBr(CH2N‐phthaloyl)(PPh3)2] (4) and trans‐[Pd{C(O)CH2N‐phthaloyl}(X)(PPh3)2] (X = Br, Cl; 5, 6). The bis(phosphane) complexes [Pd(CH2N‐phthaloyl)(X)(R2PCH2CH2PR2)] and [Pd{C(O)CH2N‐phthaloyl}(X)(R2PCH2CH2PR2)] (X = Cl, Br; R = Ph, C6H11) 8−13 were obtained by ligand exchange from 4, 5 or 6 with the corresponding bis(phosphanes). Halide abstraction from 4, 5, 6, 10, 11 or 12 gives the cationic complexes 14 and 15 with formation of a five‐membered chelate ring which includes one carbonyl atom of the phthaloyl group. The reaction of 6 with the tridentate ligand PhP(CH2CH2PPh2)2 affords the five‐coordinate complex 16 and from [Pt(C2H4)(PPh3)2] and organic halides the platinum(II) complexes trans‐[Pt(CH2N‐phthaloyl)(Cl)(PPh3)2] (17) and [PtC(O)CH(CH2Ph)N‐phthaloyl(Cl)(PPh3)2] (18) were isolated. The structures of 2, 11, 14, 15 and 16 were determined by single‐crystal X‐ray analysis. The mechanism of the palladium‐catalysed amidocarbonylation was studied using phthalimide, formaldehyde and CO as a model system which gives N‐phthaloylglycine in good yield. The proposed elementary steps in the palladium‐catalysed amidocarbonylation could be verified by use of the possible intermediates phthaloyl‐NCH2OH and phthaloyl‐NCH2Br as substrates, by oxidative addition of phthaloylmethyl bromide to Pd0, by insertion of CO into the palladium‐carbon‐bond of 4 and 8 with formation of 5 or 9, respectively, and by use of the isolated possible intermediates 4, 5 and 14 as catalysts. Thus, all crucial steps of the palladium‐catalysed amidocarbonylation with the model system phthalimide/formaldehyde/CO have been verified for the first time. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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Section: Phthalimidomethyl and ‐Acetyl Complexes Of Iron And Rhenium mentioning

confidence: 95%

Aminomethyl and Aminoacetyl Complexes of Palladium(II), Platinum(II), Iron(II) and Rhenium(I) with N‐Phthaloyl as Amino Protecting Group and Mechanistic Studies on the Palladium‐Catalyzed Amidocarbonylation

et al. 2004

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“…Thus, the acyl(aminophosphane)iron complexes [(h 5 -C 5 H 5 )Fe(CO)-(COR)(PPh 2 NR'R*)], [88±90] which correspond to the manganese complexes 23, also react in the phosphane substitution with partial retention of configuration; h 2 -acyl intermediates of type 27 ( Figure 9) have been discussed. [91] However, there has been no evidence for the formation of chiral intermediates in the phosphane substitution of the corresponding alkyl-(aminophosphane)iron complexes [(h 5 -C 5 H 5 )Fe(CO)(Me)-(PPh 2 NR'R*)] (28 a [92,93] and 28 b, [94] Scheme 10). Phosphane to the two diastereomers with opposite iron configuration in the diastereomer equilibrium.…”

Section: Complexes That Are Configurationally Labile At the Metal Atomentioning

confidence: 99%

Optically Active Organometallic Compounds of Transition Elements with Chiral Metal Atoms

Brunner¹

1999

Angew. Chem. Int. Ed.

Self Cite

323

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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“…One of the most famous and used iron catalyst for stereoselective C−C bond forming reactions is the chiral acyl‐iron complex [(η 5 ‐C 5 H 5 )Fe(CO)(COCH 3 )(PPh 3 )] ( 33 ), [61] that was prepared enantiomerically pure by resolution of the racemate and that is stable under ambient conditions (Figure 19). [62] …”

Section: Half‐sandwich Complexes In Asymmetric C−c Bond Forming React...mentioning

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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Optically active transition-metal complexes. 85. The BF3-promoted carbonylation of CpFe(CO)(L)Me compounds - a reaction stereospecific at low temperatures

Cited by 42 publications

References 5 publications

Aminomethyl and Aminoacetyl Complexes of Palladium(II), Platinum(II), Iron(II) and Rhenium(I) with N‐Phthaloyl as Amino Protecting Group and Mechanistic Studies on the Palladium‐Catalyzed Amidocarbonylation

Aminomethyl and Aminoacetyl Complexes of Palladium(II), Platinum(II), Iron(II) and Rhenium(I) with N‐Phthaloyl as Amino Protecting Group and Mechanistic Studies on the Palladium‐Catalyzed Amidocarbonylation

Optically Active Organometallic Compounds of Transition Elements with Chiral Metal Atoms

Chiral Iron Complexes in Asymmetric Organic Transformations

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