Recent Developments in the Use of <i>N</i>-Phthaloyl-Amino Acid Derivatives in Synthesis

Easton, Christopher J.; Hutton, Craig A.

doi:10.1055/s-1998-1686

Cited by 21 publications

(7 citation statements)

References 58 publications

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“…This three component reaction was discovered by Wakamatsu et al1 using octacarbonyldicobalt as a catalyst and was more recently developed into a highly efficient process with palladium catalysts 2. Here we report on the synthesis of new aminomethyl and aminoacetyl metal complexes with N ‐phthaloyl as the N ‐protecting group,3 on their role and use as catalysts in amidocarbonylation reactions and on experiments which support the mechanism of the palladium‐catalysed amidocarbonylation.…”

Section: Introductionmentioning

confidence: 83%

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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: 83%

“…The proposed mechanism of the palladium‐catalysed amidocarbonylation with aldehydes, amides and CO is shown in Scheme 3…”

Section: Experiments On the Mechanism Of The Palladium‐catalyzed Amidmentioning

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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“…Thus, like the sodiated analogue 3+Na + , the nonsodiated b-centred alanyl radical 3 has the lowest RSE of 1-3, and its reactions are calculated to be the most exothermic. The greater gas-phase reactivity of the phthalimide 2+Na + compared with the benzamide 1+Na + towards both dimethyl disulfide and 4-fluorothiophenol parallels the behaviour of acyl-and phthaloyl-glycyl radicals in solution, 12 and appears to correlate more closely with the relative RSEs and enthalpies of reactions of 2 and 1 rather than those of the sodiated analogues 2+Na + and 1+Na + (cf. reactions A+Na + /A and C+Na + /C).…”

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confidence: 81%

Gas-phase regiocontrolled generation of charged amino acid and peptide radicals

et al. 2006

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“…The phthaloyl amino protecting group is chosen to avoid any internal amine participation. Introduction of a phthaloyl protection has found great utility in synthesis (Easton and Hutton, 1998). Amine diprotection is necessary since the same reaction conducted on the N-benzyloxycarbonyl (NHCbz) and on the N-tert-butyloxycarbonyl (NHBoc) analogues did not lead to clean Rs.. co2c 3 Ncs Rs.U.…”

Section: Directly From Methioninementioning

confidence: 99%

Syntheses of optically active 2-amino-4-oxobutyric acid and N,O-protected derivatives

Meffre

1999

Amino Acids

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Strategies for the synthesis of optically active aspartaldehyde derivatives are reviewed. Most of them are using the chiral pool: allylglycine or naturally occurring homoserine, aspartic acid or methionine and side chain modifications. This will be developed in the first part. Some other original routes are also displayed in the second part. Different aspects of each strategy are discussed: the nature and number of steps, the problem of protecting groups, the price and availability of starting materials. Some synthetic applications of such interesting chiral synthons are shown in the last part.

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Recent Developments in the Use of N-Phthaloyl-Amino Acid Derivatives in Synthesis

Cited by 21 publications

References 58 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

Gas-phase regiocontrolled generation of charged amino acid and peptide radicals

Syntheses of optically active 2-amino-4-oxobutyric acid and N,O-protected derivatives

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