Convenient synthesis of optically active iron acyls

Hungate, Randall W.; Miller, Francis M.; Goodman, Murray

doi:10.1016/s0040-4039(00)80472-4

Cited by 8 publications

(2 citation statements)

References 6 publications

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“…Rhodium complexes with N ‐protected aminomethyl ligands have been prepared from [RhCp(CH 2 I)(I)(PMe 3 )] and amides 12. A general method for the preparation of η 1 ‐aminomethyl and ‐aminoacetyl complexes with a protected amino group is the reaction of anionic organometallic compounds [Co(dimethylglyoximate)] − 13 or of metal carbonyls14,15 with phthaloylmethyl halide, phthaloylglycyl chloride or with mixed anhydrides of N ‐protected α‐amino acids 16,17. The N ‐protected aminomethyl and aminoacetyl metal carbonyls can be interconverted by CO insertion14,15 or decarbonylation,14,15,17 respectively, and could be useful for the synthesis of peptides 14…”

Section: Introductionmentioning

confidence: 99%

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: Introductionmentioning

confidence: 99%

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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“…The in situ generated amino acyl iron complexes 12 were shown to react with activated α‐amino acids (mixed carbonic anhydride) to give the dipeptide derivatives 13 121…”

Section: Tiiv Zriv and Tav Amino Acid Carboxylates And Organometmentioning

confidence: 99%

Metal Complexes of Biologically Important Ligands, CLXXVI.[1] Formation of Peptides within the Coordination Sphere of Metal Ions and of Classical and Organometallic Complexes and Some Aspects of Prebiotic Chemistry

Beck

2011

Zeitschrift anorg allge chemie

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Biometallorganische Chemie – Übergangsmetallkomplexe mit α-Aminosäuren und Peptiden

Severin¹,

Bergs²,

Beck³

1998

Angewandte Chemie

105

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Ein neues interdisziplinäres Forschungsgebiet ist die Biometallorganische Chemie; sie befaßt sich mit der Einführung von metallorganischen Fragmenten in Biomoleküle (siehe z. B. Struktur rechts). Die „klassischen”︁ α‐Aminosäure‐ und Peptidliganden haben sich dabei als besonders vielseitig erwiesen und eröffnen unter anderem einen Zugang zu stereochemisch interessanten Verbindungen. α‐Aminosäuren und Peptide können durch metallorganische Verbindungen synthetisiert, markiert, stabilisiert oder aktiviert werden.

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Convenient synthesis of optically active iron acyls

Cited by 8 publications

References 6 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

Metal Complexes of Biologically Important Ligands, CLXXVI.[1] Formation of Peptides within the Coordination Sphere of Metal Ions and of Classical and Organometallic Complexes and Some Aspects of Prebiotic Chemistry

Biometallorganische Chemie – Übergangsmetallkomplexe mit α-Aminosäuren und Peptiden

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