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Amino acid N-carboxyanhydride

March 20, 2024

Amino acid N-carboxyanhydrides, also called Leuchs' anhydrides, are a family of heterocyclic organic compounds derived from amino acids. They are white, moisture-reactive solids. They have been evaluated for applications the field of biomaterials.[1][2][3]

Amino acid N-carboxyanhydride
N-Carboxyanhydrides
Formation and polymerization of an NCA.

Preparation edit

 
Glycine N-carboxyanhydride is the parent member of the amino acid N-carboxyanhydrides.

NCAs are typically prepared by phosgenation of amino acids:[4]

 

They were first synthesized by Hermann Leuchs by heating an N-ethoxycarbonyl or N-methoxycarbonyl amino acid chloride in a vacuum at 50-70 °C:[5][6]

 

A moisture-tolerant route to unprotected NCAs employs epoxides as scavengers of hydrogen chloride.[7]

This synthesis of NCAs is sometimes called the Leuchs method. The relatively high temperatures necessary for this cyclization results in the decomposition of several NCAs. Of several improvements, one notable procedure involves treating an unprotected amino acid with phosgene or its trimer.[8][9][10]

Reactions edit

NCAs are prone to hydrolysis to the parent amino acid:

RCHNHC(O)OC(O) + H2O → H2NCH(R)CO2H + CO2

Some derivatives however tolerate water briefly.[7]

NCAs convert to homopolypeptides ( [N(H)CH(R)CO)]n) through ring-opening polymerization:[1][2][3][11][12][13][14]

n RCHNHC(O)OC(O) → [N(H)CH(R)CO)]n + n CO2

Poly-L-lysine has been prepared from N-carbobenzyloxy-α-N-carboxy-L-lysine anhydride, followed by deprotection with phosphonium iodide.[15] Peptide synthesis from NCAs does not require protection of the amino acid functional groups. N-Substituted NCAs, such as sulfenamide derivatives have also been examined.[16] The ring-opening polymerization of NCAs is catalyzed by metal catalysts.[17][3][6][11]

The polymerization of NCA’s have been considered as a prebiotic route to polypeptides.[3][18] [19]

Further reading edit

  • Grazon C, Salas-Ambrosio P, Ibarboure E, Buol A, Garanger E, Grinstaff MW, et al. (January 2020). "Aqueous Ring-Opening Polymerization-Induced Self-Assembly (ROPISA) of N-Carboxyanhydrides" (PDF). Angewandte Chemie. 59 (2): 622–626. doi:10.1002/ange.201912028. PMID 31650664. S2CID 241302007.
  • iang J, Zhang X, Fan Z, Du J (2019-10-15). "Ring-Opening Polymerization of N-Carboxyanhydride-Induced Self-Assembly for Fabricating Biodegradable Polymer Vesicles". ACS Macro Letters. 8 (10): 1216–1221. doi:10.1021/acsmacrolett.9b00606. PMID 35651173. S2CID 203135939.
  • Barrett SE, Burke RS, Abrams MT, Bason C, Busuek M, Carlini E, et al. (June 2014). "Development of a liver-targeted siRNA delivery platform with a broad therapeutic window utilizing biodegradable polypeptide-based polymer conjugates". Journal of Controlled Release. 183: 124–37. doi:10.1016/j.jconrel.2014.03.028. PMID 24657948.
  • Kramer JR, Onoa B, Bustamante C, Bertozzi CR (October 2015). "Chemically tunable mucin chimeras assembled on living cells". Proceedings of the National Academy of Sciences of the United States of America. 112 (41): 12574–9. Bibcode:2015PNAS..11212574K. doi:10.1073/pnas.1516127112. PMC 4611660. PMID 26420872.

See also edit

References edit

  1. ^ a b Kramer J, Deming TJ (2020). Polypeptide Nanomaterials. Vol. 1–4. Soft Matter and Biomaterials on the Nanoscale: World Scientific. pp. 115–180. Bibcode:2020smb3.book..115K.
  2. ^ a b Whitesides GM, Grzybowski B (March 2002). "Self-assembly at all scales". Science. 295 (5564): 2418–21. Bibcode:2002Sci...295.2418W. doi:10.1126/science.1070821. PMID 11923529. S2CID 40684317.
  3. ^ a b c d Kricheldorf HR (September 2006). "Polypeptides and 100 years of chemistry of alpha-amino acid N-carboxyanhydrides". Angewandte Chemie. 45 (35): 5752–84. doi:10.1002/anie.200600693. PMID 16948174.
  4. ^ Lyndon C. Xavier, Julie J. Mohan, David J. Mathre, Andrew S. Thompson, James D. Carroll, Edward G. Corley, and Richard Desmond (1997). "(S)-Tetrahydro-1-methyl-3,3-diphenyl-1h,3h-pyrrolo-[1,2-c] [1,3,2]oxazaborole-borane Complex". Organic Syntheses. 74: 50. doi:10.15227/orgsyn.074.0050.{{cite journal}}: CS1 maint: multiple names: authors list (link)
  5. ^ Leuchs H (1906). "Ueber die Glycin-carbonsäure" [About the glycine-carboxylic acid]. Berichte der Deutschen Chemischen Gesellschaft (in German). 39: 857–61. doi:10.1002/cber.190603901133.
  6. ^ a b Deming TJ (2007). "Synthetic polypeptides for biomedical applications". Prog. Polym. Sci. 32 (8–9): 858–875. doi:10.1016/j.progpolymsci.2007.05.010.
  7. ^ a b Tian ZY, Zhang Z, Wang S, Lu H (October 2021). "A Moisture-Tolerant Route to Unprotected α/β-Amino acid N-Carboxyanhydrides and Facile Synthesis of Hyperbranched Polypeptides". Nature Communications. 12 (1): 5810. Bibcode:2021NatCo..12.5810T. doi:10.1038/s41467-021-25689-y. PMC 8490447. PMID 34608139.
  8. ^ Montalbetti CA, Falque V (2005). "Amide bond formation and peptide coupling". Tetrahedron. 61 (46): 10827–52. doi:10.1016/j.tet.2005.08.031.
  9. ^ Xavier LC, Mohan JJ, Mathre DJ, Thompson AS, Carroll JD, Corley EG, Desmond R (1997). "(S)-Tetrahydro-1-methyl-3,3-diphenyl-1h,3h-pyrrolo-[1,2-c] [1,3,2]oxazaborole-borane Complex". Org. Synth. 74: 50. doi:10.15227/orgsyn.074.0050.
  10. ^ Gibson MI, Hunt GJ, Cameron NR (September 2007). "Improved synthesis of O-linked, and first synthesis of S- linked, carbohydrate functionalised N-carboxyanhydrides (glycoNCAs)". Organic & Biomolecular Chemistry. 5 (17): 2756–7. doi:10.1039/b707563d. PMID 17700840.
  11. ^ a b Dimitrov I, Schlaad H (December 2003). "Synthesis of nearly monodisperse polystyrene-polypeptide block copolymers via polymerisation of N-carboxyanhydrides". Chemical Communications (23): 2944–2945. doi:10.1039/b308990h. PMID 14680253.
  12. ^ Song Z, Han Z, Lv S, Chen C, Chen L, Yin L, Cheng J (October 2017). "Synthetic Polypeptides: from Polymer Design to Supramolecular Assembly and Biomedical Application". Chemical Society Reviews. 46 (21): 6570–6599. doi:10.1039/C7CS00460E. PMID 28944387.
  13. ^ Kopecek J (September 2003). "Smart and genetically engineered biomaterials and drug delivery systems". European Journal of Pharmaceutical Sciences. 20 (1): 1–16. doi:10.1016/S0928-0987(03)00164-7. PMID 13678788.
  14. ^ Lu H, Wang J, Song Z, Yin L, Zhang Y, Tang H, et al. (January 2014). "Recent Advances in Amino Acid N-Carboxyanhydrides and Synthetic Polypeptides: Chemistry, Self-Assembly and Biological Applications". Chemical Communications. 50 (2): 139–55. doi:10.1039/c3cc46317f. PMID 24217557.
  15. ^ Katchalski-Katzir E (April 2005). "My contributions to science and society". The Journal of Biological Chemistry. 280 (17): 16529–41. doi:10.1074/jbc.X400013200. PMID 15718236.
  16. ^ Katakai R (September 1975). "Peptide synthesis using o-nitrophenylsulfenyl N-carboxy alpha-amino acid anhydrides". The Journal of Organic Chemistry. 40 (19): 2697–2702. doi:10.1021/jo00907a001. PMID 1177065.
  17. ^ Deming TJ (1998). "Amino Acid Derived Nickelacycles: Intermediates in Nickel-Mediated Polypeptide Synthesis". Journal of the American Chemical Society. 120 (17): 4240–4241. doi:10.1021/ja980313i.
  18. ^ Taillades J, Beuzelin I, Garrel L, Tabacik V, Bied C, Commeyras A (February 1998). "N-carbamoyl-alpha-amino acids rather than free alpha-amino acids formation in the primitive hydrosphere: a novel proposal for the emergence of prebiotic peptides". Origins of Life and Evolution of the Biosphere. 28 (1): 61–77. Bibcode:1998OLEB...28...61T. doi:10.1023/A:1006566810636. PMID 11536856. S2CID 22189268.
  19. ^ Ferris JP, Hill AR, Liu R, Orgel LE (May 1996). "Synthesis of long prebiotic oligomers on mineral surfaces". Nature. 381 (6577): 59–61. Bibcode:1996Natur.381...59F. doi:10.1038/381059a0. hdl:2060/19980119839. PMID 8609988. S2CID 4351826.

March 20, 2024
amino, acid, carboxyanhydride, also, called, leuchs, anhydrides, family, heterocyclic, organic, compounds, derived, from, amino, acids, they, white, moisture, reactive, solids, they, have, been, evaluated, applications, field, biomaterials, carboxyanhydridesfo. Amino acid N carboxyanhydrides also called Leuchs anhydrides are a family of heterocyclic organic compounds derived from amino acids They are white moisture reactive solids They have been evaluated for applications the field of biomaterials 1 2 3 Amino acid N carboxyanhydrideN CarboxyanhydridesFormation and polymerization of an NCA Contents 1 Preparation 2 Reactions 3 Further reading 4 See also 5 ReferencesPreparation edit nbsp Glycine N carboxyanhydride is the parent member of the amino acid N carboxyanhydrides NCAs are typically prepared by phosgenation of amino acids 4 nbsp They were first synthesized by Hermann Leuchs by heating an N ethoxycarbonyl or N methoxycarbonyl amino acid chloride in a vacuum at 50 70 C 5 6 nbsp A moisture tolerant route to unprotected NCAs employs epoxides as scavengers of hydrogen chloride 7 This synthesis of NCAs is sometimes called the Leuchs method The relatively high temperatures necessary for this cyclization results in the decomposition of several NCAs Of several improvements one notable procedure involves treating an unprotected amino acid with phosgene or its trimer 8 9 10 Reactions editNCAs are prone to hydrolysis to the parent amino acid RCHNHC O OC O H2O H2NCH R CO2H CO2Some derivatives however tolerate water briefly 7 NCAs convert to homopolypeptides N H CH R CO n through ring opening polymerization 1 2 3 11 12 13 14 n RCHNHC O OC O N H CH R CO n n CO2Poly L lysine has been prepared from N carbobenzyloxy a N carboxy L lysine anhydride followed by deprotection with phosphonium iodide 15 Peptide synthesis from NCAs does not require protection of the amino acid functional groups N Substituted NCAs such as sulfenamide derivatives have also been examined 16 The ring opening polymerization of NCAs is catalyzed by metal catalysts 17 3 6 11 The polymerization of NCA s have been considered as a prebiotic route to polypeptides 3 18 19 Further reading editGrazon C Salas Ambrosio P Ibarboure E Buol A Garanger E Grinstaff MW et al January 2020 Aqueous Ring Opening Polymerization Induced Self Assembly ROPISA of N Carboxyanhydrides PDF Angewandte Chemie 59 2 622 626 doi 10 1002 ange 201912028 PMID 31650664 S2CID 241302007 iang J Zhang X Fan Z Du J 2019 10 15 Ring Opening Polymerization of N Carboxyanhydride Induced Self Assembly for Fabricating Biodegradable Polymer Vesicles ACS Macro Letters 8 10 1216 1221 doi 10 1021 acsmacrolett 9b00606 PMID 35651173 S2CID 203135939 Barrett SE Burke RS Abrams MT Bason C Busuek M Carlini E et al June 2014 Development of a liver targeted siRNA delivery platform with a broad therapeutic window utilizing biodegradable polypeptide based polymer conjugates Journal of Controlled Release 183 124 37 doi 10 1016 j jconrel 2014 03 028 PMID 24657948 Kramer JR Onoa B Bustamante C Bertozzi CR October 2015 Chemically tunable mucin chimeras assembled on living cells Proceedings of the National Academy of Sciences of the United States of America 112 41 12574 9 Bibcode 2015PNAS 11212574K doi 10 1073 pnas 1516127112 PMC 4611660 PMID 26420872 See also editDakin West reaction Glycine N carboxyanhydride the parent NCAReferences edit a b Kramer J Deming TJ 2020 Polypeptide Nanomaterials Vol 1 4 Soft Matter and Biomaterials on the Nanoscale World Scientific pp 115 180 Bibcode 2020smb3 book 115K a b Whitesides GM Grzybowski B March 2002 Self assembly at all scales Science 295 5564 2418 21 Bibcode 2002Sci 295 2418W doi 10 1126 science 1070821 PMID 11923529 S2CID 40684317 a b c d Kricheldorf HR September 2006 Polypeptides and 100 years of chemistry of alpha amino acid N carboxyanhydrides Angewandte Chemie 45 35 5752 84 doi 10 1002 anie 200600693 PMID 16948174 Lyndon C Xavier Julie J Mohan David J Mathre Andrew S Thompson James D Carroll Edward G Corley and Richard Desmond 1997 S Tetrahydro 1 methyl 3 3 diphenyl 1h 3h pyrrolo 1 2 c 1 3 2 oxazaborole borane Complex Organic Syntheses 74 50 doi 10 15227 orgsyn 074 0050 a href Template Cite journal html title Template Cite journal cite journal a CS1 maint multiple names authors list link Leuchs H 1906 Ueber die Glycin carbonsaure About the glycine carboxylic acid Berichte der Deutschen Chemischen Gesellschaft in German 39 857 61 doi 10 1002 cber 190603901133 a b Deming TJ 2007 Synthetic polypeptides for biomedical applications Prog Polym Sci 32 8 9 858 875 doi 10 1016 j progpolymsci 2007 05 010 a b Tian ZY Zhang Z Wang S Lu H October 2021 A Moisture Tolerant Route to Unprotected a b Amino acid N Carboxyanhydrides and Facile Synthesis of Hyperbranched Polypeptides Nature Communications 12 1 5810 Bibcode 2021NatCo 12 5810T doi 10 1038 s41467 021 25689 y PMC 8490447 PMID 34608139 Montalbetti CA Falque V 2005 Amide bond formation and peptide coupling Tetrahedron 61 46 10827 52 doi 10 1016 j tet 2005 08 031 Xavier LC Mohan JJ Mathre DJ Thompson AS Carroll JD Corley EG Desmond R 1997 S Tetrahydro 1 methyl 3 3 diphenyl 1h 3h pyrrolo 1 2 c 1 3 2 oxazaborole borane Complex Org Synth 74 50 doi 10 15227 orgsyn 074 0050 Gibson MI Hunt GJ Cameron NR September 2007 Improved synthesis of O linked and first synthesis of S linked carbohydrate functionalised N carboxyanhydrides glycoNCAs Organic amp Biomolecular Chemistry 5 17 2756 7 doi 10 1039 b707563d PMID 17700840 a b Dimitrov I Schlaad H December 2003 Synthesis of nearly monodisperse polystyrene polypeptide block copolymers via polymerisation of N carboxyanhydrides Chemical Communications 23 2944 2945 doi 10 1039 b308990h PMID 14680253 Song Z Han Z Lv S Chen C Chen L Yin L Cheng J October 2017 Synthetic Polypeptides from Polymer Design to Supramolecular Assembly and Biomedical Application Chemical Society Reviews 46 21 6570 6599 doi 10 1039 C7CS00460E PMID 28944387 Kopecek J September 2003 Smart and genetically engineered biomaterials and drug delivery systems European Journal of Pharmaceutical Sciences 20 1 1 16 doi 10 1016 S0928 0987 03 00164 7 PMID 13678788 Lu H Wang J Song Z Yin L Zhang Y Tang H et al January 2014 Recent Advances in Amino Acid N Carboxyanhydrides and Synthetic Polypeptides Chemistry Self Assembly and Biological Applications Chemical Communications 50 2 139 55 doi 10 1039 c3cc46317f PMID 24217557 Katchalski Katzir E April 2005 My contributions to science and society The Journal of Biological Chemistry 280 17 16529 41 doi 10 1074 jbc X400013200 PMID 15718236 Katakai R September 1975 Peptide synthesis using o nitrophenylsulfenyl N carboxy alpha amino acid anhydrides The Journal of Organic Chemistry 40 19 2697 2702 doi 10 1021 jo00907a001 PMID 1177065 Deming TJ 1998 Amino Acid Derived Nickelacycles Intermediates in Nickel Mediated Polypeptide Synthesis Journal of the American Chemical Society 120 17 4240 4241 doi 10 1021 ja980313i Taillades J Beuzelin I Garrel L Tabacik V Bied C Commeyras A February 1998 N carbamoyl alpha amino acids rather than free alpha amino acids formation in the primitive hydrosphere a novel proposal for the emergence of prebiotic peptides Origins of Life and Evolution of the Biosphere 28 1 61 77 Bibcode 1998OLEB 28 61T doi 10 1023 A 1006566810636 PMID 11536856 S2CID 22189268 Ferris JP Hill AR Liu R Orgel LE May 1996 Synthesis of long prebiotic oligomers on mineral surfaces Nature 381 6577 59 61 Bibcode 1996Natur 381 59F doi 10 1038 381059a0 hdl 2060 19980119839 PMID 8609988 S2CID 4351826 Retrieved from https en wikipedia org w index php title Amino acid N carboxyanhydride amp oldid 1140541684, wikipedia, wiki, book, books, library,

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