Preparation of Diphenylphosphinoserine and Synthesis of Other Phosphine Containing Amino Acids Using Zinc/Copper Reagents

Greenfield, Scott J.; Gilbertson, Scott R.

doi:10.1055/s-2001-18431

Cited by 29 publications

(21 citation statements)

References 21 publications

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“…When the phosphines are positioned in an i, iþ3 relationship and the two amino acids between them are proline and a D-amino acid, the peptide adopts a -turn secondary structure and exhibits good selectivity in the reaction of cyclic allyl acetates and methyl malonate. [49][50][51] (It should be noted that Miller has used -turn structures in the development of asymmetric acylation catalysts. 33,34,52,53 ) Through the combination of different peptide sequences and different phosphine amino acids, a catalyst system was developed that provided products in high selectivity.…”

Section: Catalysis With Phosphine-containing Peptidesmentioning

confidence: 98%

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Synthesis of phosphine containing amino acids: Utilization of peptide synthesis in ligand design

et al. 2005

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Combinatorial chemistry has recently burst on the scene as a valuable tool for the discovery of new drug candidates. The ability to synthesize hundreds of compounds for screening is a useful complement to rational drug design. There are many similarities between the design of new therapeutic agents and the development of new asymmetric ligands, the most important of which is the limitation of a rational design strategy. For this reason a program was begun that would allow the use of combinatorial technology in the development of new ligands for transition metal catalyzed asymmetric reactions. Because of the large number of catalytic reactions they are involved in the system was based around phosphine ligands. This paper reports the synthesis of phosphine derivatives of alanine, proline, and the aromatic amino acids tyrosine and hydroxyphenylglycine. Examples of the use of these amino acids in the synthesis of peptides possessing helical and beta-turn secondary structures are presented. Metal complexes of these peptide-based ligands are used in hydrogenation and alkylation reactions.

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Section: Catalysis With Phosphine-containing Peptidesmentioning

confidence: 98%

“…2-tert-Butoxycarbonylamino-3-(diphenyl-phosphinothioyl)-propionic Acid Methyl Ester (13 (50). MeMgCl (3.0 M in THF, 10.6 mL, 31.79 mmol) was added to a solution of (S)-(-)-4-benzyl-2-oxazolidinone (5.522 g, 31.17 mmol) in THF (100 mL) at 08C.…”

Section: Fmoc-pps(s)-oh (14)mentioning

confidence: 99%

Synthesis of phosphine containing amino acids: Utilization of peptide synthesis in ligand design

et al. 2005

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“…[24] For this purpose several sulfur-protected phosphane-containing alanine derivatives compatible with solidphase peptide synthesis were developed (Scheme 3a). [25] In addition a phosphane-sulfide functionalised proline as alternative phosphane-peptide building blocks (Scheme 3b) and a procedure to introduce phosphane moieties into aromatic amino acids after peptide synthesis were reported (Scheme 3c). [26] Several phosphane-containing oligopeptides with a helical motif were synthesised.…”

Section: Oligopeptide-modified Phosphane Ligandsmentioning

confidence: 99%

“…[22] Scheme 3. Phosphane-containing amino acid residues synthesised by the group of Gilbertson based on a) valine, [25] b) proline and c) phenylalanine. [26] These units were applied in d) helical structures for rhodium-catalysed asymmetric hydrogenation [27] and e) proline-b-turn motifs for palladium-catalysed allylic substitution.…”

Section: Oligopeptide-modified Phosphane Ligandsmentioning

confidence: 99%

Bioinspired Catalyst Design and Artificial Metalloenzymes

Deuss

Heeten

Laan

et al. 2011

Chemistry A European J

181

124

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Many bioinspired transition-metal catalysts have been developed over the recent years. In this review the progress in the design and application of ligand systems based on peptides and DNA and the development of artificial metalloenzymes are reviewed with a particular emphasis on the combination of phosphane ligands with powerful molecular recognition and shape selectivity of biomolecules. The various approaches for the assembly of these catalytic systems will be highlighted, and the possibilities that the use of the building blocks of Nature provide for catalyst optimisation strategies are discussed.

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“…Some of these catalysts were found to show good selectivity in transformations such as hydrogenations, [25,26] allylic substitutions [27,28] and desymmetrisation of mesodiols. [29] However, although the synthesis of the diphenyland dicyclohexylphosphinoserine building blocks was recently improved, [30] resulting also in a series of new aryl phosphinoserine building blocks, [28,31] it still involves several steps and protection of the phosphine moiety. Furthermore, incorporation of different phosphinoserine residues in the peptide sequence, requires new building block synthesis for each type of phosphine moiety.…”

Section: Introductionmentioning

confidence: 99%

Efficient Solid‐Phase Synthesis of Peptide‐Based Phosphine Ligands: Towards Combinatorial Libraries of Selective Transition Metal Catalysts

Christensen

Meldal

2005

Chemistry A European J

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A new methodology for the solid-phase synthesis of peptide-based phosphine ligands has been developed. Solid supported peptide scaffolds possessing either primary or secondary amines were synthesised using commercially available Fmoc-protected amino acids and readily available Fmoc-protected amino aldehydes for reductive alkylation, in standard solid-phase peptide synthesis (SPPS). Phosphine moieties were introduced by phosphinomethylation of the free amines as the final solid-phase synthetic step, immediately prior to complexation with palladium(II), thus avoiding tedious protection/deprotection of the phosphine moieties during the synthesis of the ligands. The extensive use of commercial building blocks and standard SPPS makes this methodology well suited for the generation of solid-phase combinatorial libraries of novel ligands. Furthermore, it is possible to generate several different phosphine ligand libraries for every peptide scaffold library synthesised, by functionalising the scaffold libraries with different phosphine moieties. The synthesised ligands were characterised on solid support by conventional (31)P NMR spectroscopy and, cleaved from the support, as their phosphine oxides by HPLC, (1)H NMR, (31)P NMR and high resolution ESMS. Palladium(II) allyl complexes were generated from the resin bound ligands and to demonstrate their catalytic properties, palladium catalysed asymmetric allylic substitution reactions were performed. Good yields and moderate enantioselectivity was obtained for the selected combination of catalysts and substrate, but most importantly the concept of this new methodology was proven. Screening of ligand libraries should afford more selective catalysts.

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Preparation of Diphenylphosphinoserine and Synthesis of Other Phosphine Containing Amino Acids Using Zinc/Copper Reagents

Abstract: Primary and secondary iodo amino acids are converted to zinc iodides. The resulting organozinc iodides are reacted with copper, and then coupled with aryl and alkyl phosphine chlorides in good to moderate yields.

Cited by 29 publications

References 21 publications

Synthesis of phosphine containing amino acids: Utilization of peptide synthesis in ligand design

Synthesis of phosphine containing amino acids: Utilization of peptide synthesis in ligand design

Bioinspired Catalyst Design and Artificial Metalloenzymes

Efficient Solid‐Phase Synthesis of Peptide‐Based Phosphine Ligands: Towards Combinatorial Libraries of Selective Transition Metal Catalysts

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