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Nitrogenation Strategy for the Synthesis of Carbamides

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Nitrogenation Strategy for the Synthesis of N-containing Compounds

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Abstract

In this chapter, the synthesis of carbamides and their analogues such as carbamoyl azides through N atoms incorporation strategy with C–H and/or C–C bond cleavage is summarized. Azides considered as nitrogen sources with various oxidants are efficiently employed in these transformations. Aldehydes, ketones, alcohols, and alkynes were converted into the corresponding carbamoyl azides and carbamides efficiently through this strategy.

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References

  1. Gallou IO (2007) Unsymmetrical ureas. Synthetic methodologies and application in drug design. Org Prep Proced Int 39(43):355–383

    Article  CAS  Google Scholar 

  2. Zhang J, Zhou J, Ren X, Diao Y, Li H, Jiang H, Ding K, Pei D (2012) A new diaryl urea compound, D181, induces cell cycle arrest in the G1 and M phases by targeting receptor tyrosine kinases and the microtubule skeleton. Invest New Drugs 30(2):490–507

    Article  CAS  Google Scholar 

  3. Anandan S-K, Webb HK, Do ZN, Gless RD (2009) Unsymmetrical non-adamantyl N,N′-diaryl urea and amide inhibitors of soluble expoxide hydrolase. Bioorg Med Chem Lett 19(15):4259–4263

    Article  CAS  Google Scholar 

  4. Tai-The W, Huang J, Arrington ND, Dill GM (1987) Synthesis and herbicidal activity of.alpha.-heterocyclic carbinol carbamates. J Agric Food Chem 35(5):817–823

    Article  Google Scholar 

  5. Chaturvedi D, Mishra N, Mishra V (2007) Various approaches for the synthesis of organic carbamates. Curr Org Synth 4:308–320

    Article  CAS  Google Scholar 

  6. Clayden J, Hennecke U (2008) α-Pyridylation of chiral amines via urea coupling, lithiation and rearrangement. Org Lett 10(16):3567–3570

    Article  CAS  Google Scholar 

  7. Lefranc J, Tetlow DJ, Donnard M, Minassi A, Galvez E, Clayden J (2011) Geometry-Selective synthesis of E or Z N-vinyl ureas (N-carbamoyl enamines). Org Lett 13(2):296–299

    Article  CAS  Google Scholar 

  8. Yu S, Haight A, Kotecki B, Wang L, Lukin K, Hill DR (2009) Synthesis of a TRPV1 receptor antagonist. J Org Chem 74(24):9539–9542

    Article  CAS  Google Scholar 

  9. Ali A, Reddy GSKK, Nalam MNL, Anjum SG, Cao H, Schiffer CA, Rana TM (2010) Structure-based design, synthesis, and structure–activity relationship studies of HIV-1 protease inhibitors incorporating phenyloxazolidinones. J Med Chem 53(21):7699–7708

    Article  CAS  Google Scholar 

  10. Lieber E, Minnis RLJ, Rao CNR (1965) Carbamoyl azides. Chem Rev 65(3):377–384

    Article  CAS  Google Scholar 

  11. Doyle AG, Jacobsen EN (2007) Small-molecule H-bond donors in asymmetric catalysis. Chem Rev 107(12):5713–5743

    Article  CAS  Google Scholar 

  12. Yang T, Ferrali A, Sladojevich F, Campbell L, Dixon DJ (2009) Brønsted base/lewis acid cooperative catalysis in the enantioselective conia-ene reaction. J Am Chem Soc 131(26):9140–9141

    Article  CAS  Google Scholar 

  13. Adams P, Baron FA (1965) Esters of carbamic acid. Chem Rev 65(5):567–602

    Article  CAS  Google Scholar 

  14. Chaturvedi D (2011) Recent developments on the carbamation of amines. Curr Org Chem 15(10):1593–1624

    Article  CAS  Google Scholar 

  15. Ulrich H (1997) Chemistry and technology of isocyanates. Wiley, Chichester

    Google Scholar 

  16. Slocombe RJ, Hardy EE, Saunders JH, Jenkins RL (1950) Phosgene derivatives. the preparation of isocyanates, carbamyl chlorides and cyanuric acid. J Am Chem Soc 72(5):1888–1891

    Article  CAS  Google Scholar 

  17. Eckert H, Forster B (1987) Triphosgene, a crystalline phosgene substitute. Angew Chem Int Ed 26(9):894–895

    Article  Google Scholar 

  18. Batey RA, Santhakumar V, Yoshina-Ishii C, Taylor SD (1998) An efficient new protocol for the formation of unsymmetrical tri- and tetrasubstituted ureas. Tetrahedron Lett 39(35):6267–6270

    Article  CAS  Google Scholar 

  19. Babad H, Zeiler AG (1973) Chemistry of phosgene. Chem Rev 73(1):75–91

    Article  CAS  Google Scholar 

  20. Norwick JS, Powell NA, Nguyen TM, Noronha G (1992) An improved method for the synthesis of enantiomerically pure amino acid ester isocyanates. J Org Chem 57(26):7364–7366

    Article  Google Scholar 

  21. Shimizu M, Sodeoka M (2007) Convenient method for the preparation of carbamates, carbonates, and thiocarbonates. Org Lett 9(25):5231–5234

    Article  CAS  Google Scholar 

  22. Kim JG, Jang DO (2009) Indium-catalyzed reaction for the synthesis of carbamates and carbonates: selective protection of amino groups. Tetrahedron Lett 50(22):2688–2692

    Article  CAS  Google Scholar 

  23. Paul F (2000) Catalytic synthesis of isocyanates or carbamates from nitroaromatics using group viii transition metal catalysts. Coord Chem Rev 203(1):269–323

    Article  CAS  Google Scholar 

  24. Dieck HA, Laine RM, Heck RF (1975) Low-pressure, palladium-catalyzed N,N′-diarylurea synthesis from nitro compounds, amines, and carbon monoxide. J Org Chem 40(19):2819–2822

    Article  CAS  Google Scholar 

  25. Kim KD, Lee SM, Cho NS, Oh JS, Lee CW, Lee JS (1992) Palladium-catalyzed N,N′-diphenylurea synthesis from nitrobenzene, aniline, and carbon monoxide. Part 3. Evidence of carbamoyl intermediate. J Mol Catal 75(1):L1–L6

    Article  CAS  Google Scholar 

  26. Gasperini M, Ragaini F, Remondini C, Caselli A, Cenini S (2005) The palladium–phenanthroline catalyzed carbonylation of nitroarenes to diarylureas: effect of chloride and diphenylphosphinic acid. J Organomet Chem 690(20):4517–4529

    Article  CAS  Google Scholar 

  27. Banthorpe DV (1971) Rearrangements involving azido groups. In: Patai S (ed) The chemistry of the azido group. Wiley, New York, pp 397–400

    Google Scholar 

  28. Yagodkin A, Löschcke K, Weisell J, Azhayev A (2010) Straightforward carbamoylation of nucleophilic compounds employing organic azides, phosphines, and aqueous trialkylammonium hydrogen carbonate. Tetrahedron 66(12):2210–2221

    Article  CAS  Google Scholar 

  29. Breitler S, Oldenhuis NJ, Fors BP, Buchwald SL (2011) Synthesis of unsymmetrical diarylureas via Pd-catalyzed C–N cross-coupling reactions. Org Lett 13(12):3262–3265

    Article  CAS  Google Scholar 

  30. Hooker JM, Reibel AT, Hill SM, Schueller MJ, Fowler JS (2009) One-Pot, Direct Incorporation of [11C]CO2 into Carbamates. Angew Chem Int Ed 48(19):3482–3485

    Article  CAS  Google Scholar 

  31. Peterson SL, Stucka SM, Dinsmore CJ (2010) Parallel synthesis of ureas and carbamates from amines and CO2 under mild conditions. Org Lett 12(6):1340–1343

    Article  CAS  Google Scholar 

  32. Wei Y, Liu J, Lin S, Ding H, Liang F, Zhao B (2010) Acetoacetanilides as masked isocyanates: facile and efficient synthesis of unsymmetrically substituted ureas. Org Lett 12(19):4220–4223

    Article  CAS  Google Scholar 

  33. Dube P, Nathel NFF, Vetelino M, Couturier M, Aboussafy CL, Pichette S, Jorgensen ML, Hardink M (2009) Carbonyldiimidazole-mediated lossen rearrangement. Org Lett 11(24):5622–5625

    Article  CAS  Google Scholar 

  34. Hutchby M, Houlden CE, Ford JG, Tyler SNG, Gagne MR, Lloyd-Jones GC, Booker-Milburn KI (2009) Hindered ureas as masked isocyanates: facile carbamoylation of nucleophiles under neutral conditions. Angew Chem Int Ed 48(46):8721–8724

    Article  CAS  Google Scholar 

  35. Scriven EFV, Turnbull K (1988) Azides: their preparation and synthetic uses. Chem Rev 88(2):297–368

    Article  CAS  Google Scholar 

  36. Brase S, Gil C, Knepper K, Zimmermann V (2005) Organic azides: an exploding diversity of a unique class of compounds. Angew Chem Int Ed 44(33):5188–5240

    Article  CAS  Google Scholar 

  37. Brase S, Banert K (2010) Organic azides: syntheses and applications. Wiley, Chichester

    Google Scholar 

  38. Katritzky AR, Widyan K, Kirichenko K (2007) Preparation of polyfunctional acyl azides. J Org Chem 72(15):5802–5804

    Article  CAS  Google Scholar 

  39. Chen DJ, Chen ZC (2000) Hypervalent iodine in synthesis. Part 54: one-step conversion of aryl aldehydes to aroyl azides using a combined reagent of (diacetoxyiodo)benzene with sodium azide. Tetrahedron Lett 41(38):7361–7363

    Article  CAS  Google Scholar 

  40. Pedersen MC, Marinescu LG, Bols M (2005) Radical substitution with azide: TMSN3–PhI(OAc)2 as a substitute of IN3. Org Biomol Chem 3(5):816–822

    Article  CAS  Google Scholar 

  41. Marinescu L, Thinggaard J, Thomsen IB, Bols M (2003) Radical azidonation of aldehydes. J Org Chem 68(24):9453–9455

    Article  CAS  Google Scholar 

  42. Marinescu LG, Pedersen MC, Bols M (2005) Safe radical azidonation using polystyrene supported diazidoiodate(I). Tetrahedron 61(1):123–127

    Article  CAS  Google Scholar 

  43. Sarkar SD, Studer A (2010) Oxidative amidation and azidation of aldehydes by NHC catalysis. Org Lett 12(9):1992–1995

    Article  Google Scholar 

  44. Feng P, Sun X, Su Y, Li X, Zhang LH, Shi X, Jiao N (2014) Ceric ammonium nitrate (CAN) catalyzed modification of ketones via two C–C bond cleavages with the retention of the oxo-group. Org Lett 16(12):3388–3391

    Article  CAS  Google Scholar 

  45. Feng P, Zou M, Jiao N, KI/TBHP catalyzed nitrogenation of aldehydes or alcohols: the direct synthesis of carbamoyl azides and ureas. Unpublished work

    Google Scholar 

  46. Qin C, Su Y, Shen T, Shi X, Jiao N (2016) Splitting a substrate into three parts: gold-catalyzed nitrogenation of alkynes by C–C and C≡C bond cleavage. Angew Chem Int Ed 55(1):350–354

    Article  CAS  Google Scholar 

  47. Guan Z-H, Lei H, Chen M, Ren Z-H, Bai Y, Wang Y-Y (2012) Palladium-catalyzed carbonylation of amines: switchable approaches to carbamates and N,N′-disubstituted ureas. Adv Synth Catal 354(2–3):489–496

    Article  CAS  Google Scholar 

  48. Ren L, Jiao N (2014) PdCl2 catalyzed efficient assembly of organic azides, CO, and alcohols under mild conditions: a direct approach to synthesize carbamates. Chem Commun 50(28):3706–3709

    Article  CAS  Google Scholar 

  49. Zhang Z, Li Z, Fu B, Zhang Z (2015) Palladium-catalyzed cross-coupling reaction of azides with isocyanides. Chem Commun 51(91):16312–16315

    Article  CAS  Google Scholar 

  50. Vinogradova EV, Fors BP, Buchwald SL (2012) Palladium-catalyzed cross-coupling of aryl chlorides and triflates with sodium cyanate: a practical synthesis of unsymmetrical ureas. J Am Chem Soc 134(27):11132–11135

    Article  CAS  Google Scholar 

  51. Zhao J, Li Z, Song S, Wang M-A, Fu B, Zhang Z (2016) Product-derived bimetallic palladium complex catalyzes direct carbonylation of sulfonylazides. Angew Chem Int Ed 55(18):5545–5549

    Article  CAS  Google Scholar 

  52. Zhao J, Li Z, Yan S, Xu S, Wang M-A, Fu B, Zhang Z (2016) Pd/C catalyzed carbonylation of azides in the presence of amines. Org Lett 18(8):1736–1739

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Xue Yuan Rd. 38, Beijing, 100191, China

    Xinyao Li & Ning Jiao

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  1. Xinyao Li
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  2. Ning Jiao
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Correspondence to Ning Jiao .

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  1. School of Pharmaceutical Sciences, Peking University School of Pharmaceutical Sciences, Beijing, China

    Ning Jiao

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Li, X., Jiao, N. (2017). Nitrogenation Strategy for the Synthesis of Carbamides. In: Jiao, N. (eds) Nitrogenation Strategy for the Synthesis of N-containing Compounds. Springer, Singapore. https://doi.org/10.1007/978-981-10-2813-7_5

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