Skip to main content
SpringerLink
Log in

Copper-Catalyzed α-Amination of Phosphonates and Phosphine Oxides: A Direct Approach to α-Amino Phosphonic Acids and Derivatives

  • Chapter
  • First Online:
Copper-Catalyzed Electrophilic Amination of sp2 and sp3 C−H Bonds

Part of the book series: Springer Theses ((Springer Theses))

  • 458 Accesses

Abstract

A direct approach to important α-amino phosphonic acid derivatives has been developed by using copper-catalyzed electrophilic amination of α-phosphonate zincates with O-acyl hydroxylamines. This amination provides the first example of C–N bond formation which directly introduces acyclic and cyclic amines to the α-position of phosphonates in one step. The reaction also demonstrates high efficiency on a broad phosphonate substrate scope.

Portions of this chapter have been published: (a) McDonald, S. L.; Wang, Q. “Copper-Catalyzed α-Amination of Phosphonates and Phosphine Oxides: A Direct Approach to α-Amino Phosphonic Acids and Derivatives,” Angew. Chem. Int. Ed. 2014, 53, 1867–1871; (b) McDonald, S. L.; Wang, Q. “α-Amination of Phosphonates: A Direct Synthesis of α-Amino Phosphonic Acids and Their Derivatives,” Synlett 2014, 25, 2233–2238.

This is a preview of subscription content, log in via an institution to check access.

Access this chapter

Log in via an institution
eBook
USD 16.99
Price excludes VAT (USA)
  • Available as EPUB and PDF
  • Read on any device
  • Instant download
  • Own it forever
Softcover Book
USD 109.99
Price excludes VAT (USA)
  • Compact, lightweight edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info
Hardcover Book
USD 109.99
Price excludes VAT (USA)
  • Durable hardcover edition
  • Dispatched in 3 to 5 business days
  • Free shipping worldwide - see info

Tax calculation will be finalised at checkout

Purchases are for personal use only

Institutional subscriptions

References

  1. Mucha A, Kafarski P, Berlicki L (2011) Remarkable potential of the α-Aminophosphonate/Phosphinate structural motif in medicinal chemistry. J Med Chem 54(17):5955–5980

    Google Scholar 

  2. Forlani G, Berlicki L, Duo M, Dziedziola G, Giberti S, Bertazzini M, Kafarski P (2013) Synthesis and evaluation of effective inhibitors of plant δ1-Pyrroline-5-Carboxylate reductase. J Agric Food Chem 61(28):6792–6798

    Google Scholar 

  3. Forlani G, Occhipinti A, Berlicki L, Dziedziola G, Wieczorek A, Kafarski P (2008) Tailoring the structure of aminobisphosphonates to target plant P5C reductase. J Agric Food Chem 56(9):3193–3199

    Google Scholar 

  4. Allen JG, Atherton FR, Hall MJ, Hassall CH, Holmes SW, Lambert RW, Nisbet LJ, Ringrose PS (1978) Phosphonopeptides, a new class of synthetic antibacterial agents. Nature 272:56–58

    Google Scholar 

  5. Atherton FR, Hassall CH, Lambert RW (1986) Synthesis and structure-activity relationships of antibacterial phosphonopeptides incorporating (1-aminoethyl)phosphonic acid and (aminomethyl)phosphonic acid. J Med Chem 29(1):29–40

    Google Scholar 

  6. Chen MH, Chen Z, Song BA, Bhadury PS, Yang S, Cai XJ, Hu DY, Xue W, Zeng S (2009) Synthesis and antiviral activities of Chiral Thiourea derivatives containing an α-Aminophosphonate Moiety. J Agric Food Chem 57(4):1383–1388

    Google Scholar 

  7. Hu DY, Wan QQ, Yang S, Song BA, Bhadury PS, Jin LH, Yan K, Liu F, Chen Z, Xue W (2008) Synthesis and Antiviral activities of Amide derivatives containing the α-Aminophosphonate Moiety. J Agric Food Chem 56(3):998–1001

    Google Scholar 

  8. Long N, Cai X-J, Song BA, Yang S, Chen Z, Bhadury PS, Hu DY, Jin L-H, Xue W (2008) Synthesis and Antiviral Activities of Cyanoacrylate derivatives containing an α-Aminophosphonate Moiety. J Agric Food Chem 56(13):5242–5246

    Google Scholar 

  9. Kafarski P, Lejczak B (2001) Aminophosphonic acids of potential medical importance. Curr Med Chem Anticancer Agents 1(3):301–312

    Google Scholar 

  10. Lavielle G, Hautefaye P, Schaeffer C, Boutin JA, Cudennec CA, Pierre A (1991) New α-Amino phosphonic acid-derivatives of Vinblastine - chemistry and Antitumor-activity. J Med Chem 34(7):1998–2003

    Google Scholar 

  11. Allen MC, Fuhrer W, Tuck B, Wade R, Wood JM (1989) Renin inhibitors. Synthesis of transition-state analog inhibitors containing phosphorus acid derivatives at the scissile bond. J Med Chem 32(7):1652–1661

    Google Scholar 

  12. Bird J, Demello RC, Harper GP, Hunter DJ, Karran EH, Markwell RE, Mileswilliams AJ, Rahman SS, Ward RW (1994) Synthesis of novel N-phosphonoalkyl dipeptide inhibitors of human collagenase. J Med Chem 37(1):158–169

    Google Scholar 

  13. Smith WW, Bartlett PA (1998) Macrocyclic inhibitors of penicillopepsin. 3. design, synthesis, and evaluation of an inhibitor bridged between P2 and P1’. J Am Chem Soc 120(19):4622–4628

    Google Scholar 

  14. Kafarski P, Lejczak B (1991) Biological activity of aminophosphonic acids. Phosphorus Sulfur 63:193–215

    Google Scholar 

  15. Kudzin ZH, Kudzin MH, Drabowicz J, Stevens CV (2011) Aminophosphonic acids - Phosphorus analogues of natural amino acids. Part 1: Syntheses of α-Aminophosphonic acids. Curr Org Synth 15(12):2015–2071

    Google Scholar 

  16. Kukhar VP, Soloshonok VA, Solodenko VA (1994) Asymmetric-synthesis of phosphorus analogs of amino-acids. Phosphorus Sulfur 92:239–264

    Google Scholar 

  17. Denmark SE, Chatani N, Pansare SV (1992) Asymmetric electrophilic amination of Chiral phosphorus-stabilized Anions. Tetrahedron 489(11):2191–2208

    Google Scholar 

  18. Hanessian S, Bennani YL (1994) Electrophilic Amination and Azidation of Chiral α-Alkyl phosphonamides: Asymmetric syntheses of α-Amino α-Alkyl phosphonic acids. Synthesis 1994(12):1272–1274

    Google Scholar 

  19. Bernardi L, Zhuang W, Jørgensen KA (2005) An easy approach to optically active α-Amino phosphonic acid derivatives by Chiral Zn(II)-Catalyzed enantioselective amination of phosphonates. J Am Chem Soc 127(16):5772–5773

    Google Scholar 

  20. Pudovik AN (1952) Dokl Akad Nauk SSSR 74:1528

    Google Scholar 

  21. Pudovik AN, Konovalova I (1979) Addition reactions of Esters of phosphorus(III) acids with unsaturated systems. Synthesis 1979(2):81

    Google Scholar 

  22. Sasai H, Arai S, Tahara Y, Shibasaki M (1995) Catalytic asymmetric synthesis of α-Amino phosphonates using Lanthanoid-Potassium-BINOL complexes. J Org Chem 60(21):6656–6657

    Google Scholar 

  23. Smith AB, Yager KM, Taylor CM (1995) Enantioselective synthesis of diverse α-Amino phosphonate diesters. J Am Chem Soc 117(44):10879–10888

    Google Scholar 

  24. Lefebvre IM, Evans SA (1997) Studies toward the asymmetric synthesis of α-Amino phosphonic acids via the addition of phosphites to Enantiopure Sulfinimines. J Org Chem 62(22):7532–7533

    Google Scholar 

  25. Davis FA, Lee S, Yan H, Titus DD (2001) Asymmetric synthesis of quaternary α-Amino phosphonates using Sulfinimines. Org Lett 3(11):1757–1760

    Google Scholar 

  26. Joly GD, Jacobsen EN (2004) Thiourea-Catalyzed Enantioselective Hydrophosphonylation of Imines: Practical access to enantiomerically enriched α-Amino phosphonic acids. J Am Chem Soc 126(13):4102–4103

    Google Scholar 

  27. Abell JP, Yamamoto H (2008) Catalytic enantioselective pudovik reaction of Aldehydes and Aldimines with Tethered Bis(8-quinolinato) (TBOx) Aluminum complex. J Am Chem Soc 130(32):10521–10523

    Google Scholar 

  28. Nakamura S, Hayashi M, Hiramatsu Y, Shibata N, Funahashi Y, Toru T (2009) Catalytic Enantioselective Hydrophosphonylation of Ketimines using Cinchona Alkaloids. J Am Chem Soc 131(51):18240–1841

    Google Scholar 

  29. Ingle GK, Liang YX, Mormino MG, Li GL, Fronczek FR, Antilla JC (2011) Chiral Magnesium BINOL phosphate-catalyzed phosphination of imines: Access to enantioenriched α-Amino phosphine oxides. Org Lett 13(6):2054–2057

    Google Scholar 

  30. Gao Y, Huang Z, Zhuang R, Xu J, Zhang P, Tang G, Zhao Y (2013) Direct transformation of Amides into α-Amino phosphonates via a reductive phosphination process. Org Lett 15(16):4214–4217

    Google Scholar 

  31. Fields EK (1952) The synthesis of esters of substituted Amino phosphonic acids. J Am Chem Soc 74(6):1528–1531

    Google Scholar 

  32. Kabachnik MI, Medved TY (1953) New method for the synthesis of 1-aminoalkylphosphonic acids. Bull Acad Sci USSR 2(5):769–777

    Google Scholar 

  33. Cheng X, Goddard R, Buth G, List B (2008) Direct catalytic asymmetric three-component Kabachnik–fields reaction. Angew Chem Int Ed 47(27):5079–5081

    Google Scholar 

  34. Hanessian S, Bennani YL (1990) A versatile asymmetric synthesis of α-Amino α-Alkyl-phosphonic acids of high enantiomeric purity. Tetrahedron Lett 31(45):6465–6468

    Google Scholar 

  35. Groth U, Richter L, Schollkopf U (1992) Asymmetric-synthesis of enantiomerically pure phosphonic analogs of Glutamic-acid and proline. Tetrahedron 48(1):117–122

    Google Scholar 

  36. Hannour S, Roumestant ML, Viallefont P, Riche C, Martinez J, El Hallaoui A, Ouazzani F (1998) Asymmetric synthesis of (2S,3R,4R)-ethoxycarbonylcyclopropyl phosphonoglycine. Tetrahedron: Asymmetry 9(13):2329–2332

    Google Scholar 

  37. Kobayashi S, Kiyohara H, Nakamura Y, Matsubara R (2004) Catalytic asymmetric synthesis of α-Amino phosphonates using enantioselective carbon-carbon bond-forming reactions. J Am Chem Soc 126(21):6558–6559

    Google Scholar 

  38. Burk MJ, Stammers TA, Straub JA (1999) Enantioselective synthesis of α-Hydroxy and α-Amino phosphonates via catalytic asymmetric Hydrogenation. Org Lett 1(3):387–390

    Google Scholar 

  39. Hammerschmidt F, Hanbauer M (2000) Transformation of Arylmethylamines into α-Aminophosphonic acids via metalated phosphoramidates: rearrangement of partly configurationally stable N-Phosphorylated α-Aminocarbanions. J Org Chem 65(19):6121–6131

    Google Scholar 

  40. Gridnev ID, Yasutake M, Imamoto T, Beletskaya IPP (2004) Asymmetric hydrogenation of α,β-unsaturated phosphonates with Rh-BisP* and Rh-MiniPHOS catalysts: Scope and mechanism of the reaction. Proc Natl Acad Sci USA 101(15):5385–5390

    Google Scholar 

  41. Goulioukina NS, Shergold IA, Bondarenko GN, Ilyin MM, Davankov VA, Beletskaya IP (2012) Palladium-Catalyzed Asymmetric Hydrogenation of N-Hydroxy-α-imino Phosphonates using Brønsted acid as activator: The first catalytic Enantioselective approach to Chiral N-Hydroxy-α-Amino phosphonates. Adv Synth Catal 354(14–15):2727–2733

    Google Scholar 

  42. Jommi G, Miglierini G, Pagliarin R, Sello G, Sisti M (1992) Studies toward a model for predicting the Diastereoselectivity in the electrophilic amination of Chiral 1,3,2-Oxazaphospholanes. Tetrahedron 48(35):7275–7288

    Google Scholar 

  43. Pagliarin R, Papeo G, Sello G, Sisti M, Paleari L (1996) Design of β-amino alcohols as chiral auxiliaries in the electrophilic amination of 1,3,2-oxazaphospholanes. Tetrahedron 52(43):13783–13794

    Google Scholar 

  44. Jiang Q, Ren Y, Feng J (2008) Direct binding with histone deacetylase 6 mediates the reversible recruitment of parkin to the centrosome. J Neurosci 28(48):12993–13002

    Google Scholar 

  45. Naydenova ED, Todorov PT, Troev KD (2010) Recent synthesis of aminophosphonic acids as potential biological importance. Amino Acids 38(1):23–30

    Google Scholar 

  46. Ordonez M, Rojas-Cabrera H, Cativiela C (2009) An overview of Stereoselective synthesis of α-Aminophosphonic acids and derivatives. Tetrahedron 65(1):17–49

    Google Scholar 

  47. Berman AM, Johnson JS (2004) Copper-catalyzed electrophilic amination of diorganozinc reagents. J Am Chem Soc 126(18):5680–5681

    Google Scholar 

  48. Berman AM, Johnson JS (2005) Copper-catalyzed electrophilic amination of functionalized Diarylzinc reagents. J Org Chem 70(1):364–366

    Google Scholar 

  49. Berman AM, Johnson JS (2005) Nickel-catalyzed electrophilic amination of organozinc halides. Synlett 2005(11):1799–1801

    Google Scholar 

  50. Berman AM, Johnson JS (2006) Copper-catalyzed electrophilic amination of organozinc nucleophiles: Documentation of O-Benzoyl Hydroxylamines as broadly useful R2N(+) and RHN(+) Synthons. J Org Chem 71(1):219–224

    Google Scholar 

  51. Hlavinka ML, Hagadorn JR (2006) Structures of Zinc Ketone Enolates. Organometallics 25(14):3501–3507

    Google Scholar 

  52. Hlavinka ML, Hagadorn JR (2007) Zn(tmp)2: A versatile base for the selective functionalization of C−H Bonds. Organometallics 26(17):4105–4108

    Google Scholar 

  53. Rees WS, Just O, Schumann H, Weimann R (1998) First structural characterization of a zinc-bis(dialkylamide) compound. Polyhedron 17(5–6):1001–1004

    Google Scholar 

  54. Matsuda N, Hirano K, Satoh T, Miura M (2012) Copper-catalyzed amination of Arylboronates with N,N-Dialkylhydroxylamines. Angew Chem Int Ed 51(15):3642–3645

    Google Scholar 

  55. Noack M, Göttlich R (2002) Copper(I) catalysed cyclisation of unsaturated N-Benzoyloxyamines: An Aminohydroxylation via radicals. Chem Commun 2002(5):536–537

    Google Scholar 

  56. Haas B, Mosrin M, Ila H, Malakhov V, Knochel P (2011) Regio- and chemoselective metalation of Arenes and Heteroarenes using hindered metal Amide bases. Angew Chem Int Ed 50(42):9794–9824

    Google Scholar 

  57. Bresser T, Monzon G, Mosrin M, Knochel P (2010) Scaleable preparation of sensitive functionalized Aromatics and Heteroaromatics via directed metalation using tmpZnCl·LiCl. Org Process Res Dev 14(6):1299–1303

    Google Scholar 

  58. Bresser T, Mosrin M, Monzon G, Knochel P (2010) Regio- and Chemoselective Zincation of sensitive and moderately activated Aromatics and Heteroaromatics using TMPZnCl·LiCl. J Org Chem 75(14):4686–4695

    Google Scholar 

  59. Mosrin M, Bresser T, Knochel P (2009) Regio- and Chemoselective multiple functionalization of Chloropyrazine derivatives. Application to the synthesis of Coelenterazine. Org Lett 11(15):3406–3409

    Google Scholar 

  60. Mosrin M, Knochel P (2009) TMPZnCl·LiCl: A new active selective base for the directed Zincation of sensitive aromatics and Heteroaromatics. Org Lett 11(8):1837–1840

    Google Scholar 

  61. Unsinn A, Ford MJ, Knochel P (2013) New preparation of TMPZnCl·LiCl by Zn insertion into TMPCl. Application to the functionalization of dibromodiazines. Org Lett 15(5):1128–1131

    Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Department of Chemistry, Duke University, Durham, NC, USA

    Stacey L. McDonald

Authors
  1. Stacey L. McDonald
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Stacey L. McDonald .

Rights and permissions

Reprints and permissions

Copyright information

© 2016 Springer International Publishing Switzerland

About this chapter

Cite this chapter

McDonald, S.L. (2016). Copper-Catalyzed α-Amination of Phosphonates and Phosphine Oxides: A Direct Approach to α-Amino Phosphonic Acids and Derivatives. In: Copper-Catalyzed Electrophilic Amination of sp2 and sp3 C−H Bonds. Springer Theses. Springer, Cham. https://doi.org/10.1007/978-3-319-38878-6_3

Download citation

Publish with us

Policies and ethics

Search

Navigation