Download PDF
Synlett 2010(7): 1104-1106  
DOI: 10.1055/s-0029-1219566
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Symmetrical Ureas by (Diacetoxyiodo)benzene-Induced Hofmann Rearrangement

Dirk Landsberg, Markus Kalesse*
Institut für Organische Chemie, Leibniz Universität Hannover, Schneiderberg 1B, 30167 Hannover, Germany
Fax: +49(511)7623011; e-Mail: Markus.Kalesse@oci.uni-hannover.de;
Further Information

Publication History

Received 22 January 2010
Publication Date:
02 March 2010 (online)

    Permissions and Reprints All articles of this category

Abstract

Amides undergo Hofmann rearrangement by treatment with (diacetoxyiodo)benzene (DAIB) to provide symmetrical ureas in a simple and robust transformation.

Key words

Hofmann rearrangement - ureas - carbamates - diacetoxy­iodobenzene

    References and Notes

  • 1a Vachal P. Jacobsen EN. J. Am. Chem. Soc.  2002,  124:  10012 
    Google Scholar
  • 1b Yang D. Chen Y.-C. Zhu N.-Y. Org. Lett.  2004,  6:  1577 
    Google Scholar
  • 1c Taylor MS. Jacobsen EN. J. Am. Chem. Soc.  2004,  126:  10558 
    Google Scholar
  • 1d Yoon TP. Jacobsen EN. Angew. Chem. Int. Ed.  2005,  44:  466 
    Google Scholar
  • 1e Fuerst DE. Jacobsen EN. J. Am. Chem. Soc.  2005,  127:  8964 
    Google Scholar
  • 1f McCooey SH. Connon SJ. Angew. Chem. Int. Ed.  2005,  44:  6367 
    Google Scholar
  • 1g Taylor MS. Tokunaga N. Jacobsen EN. Angew. Chem. Int. Ed.  2005,  44:  6700 
    Google Scholar
  • 1h Xu X. Furukawa T. Okino T. Miyabe H. Takemoto Y. Chem. Eur. J.  2006,  12:  466 
    Google Scholar
  • 1i Lalonde MP. Chen Y. Jacobsen EN. Angew. Chem. Int. Ed.  2006,  45:  6366 
    Google Scholar
  • 1j Han C. Porco JA. Org. Lett.  2007,  9:  1517 
    Google Scholar
  • 1k Tan KL. Jacobsen EN. Angew. Chem. Int. Ed.  2007,  46:  1315 
    Google Scholar
  • 1l Procuranti B. Connon SJ. Chem. Commun.  2007,  1421 
    Google Scholar
  • 1m Shi Y.-L. Shi M. Adv. Synth. Catal.  2007,  349:  2129 
    Google Scholar
  • 1n Rampalakos C. Wulff WD. Adv. Synth. Catal.  2008,  350:  1785 
    Google Scholar
  • 1o Yalalov DA. Tsogoeva SB. Shubina TE. Martynova IM. Clark T. Angew. Chem. Int. Ed.  2008,  47:  6624 
    Google Scholar
  • 1p Fang Y.-Q. Jacobsen EN. J. Am. Chem. Soc.  2008,  130:  5660 
    Google Scholar
  • 1q Andrés JM. Manzano R. Pedrosa R. Chem. Eur. J.  2008,  14:  5116 
    Google Scholar
  • 1r Reisman SE. Doyle AG. Jacobsen EN. J. Am. Chem. Soc.  2008,  130:  7198 
    Google Scholar
  • 1s Alemán J. Milelli A. Cabrera S. Reyes E. Jørgensen KA. Chem. Eur. J.  2008,  14:  10958 
    Google Scholar
  • 1t Kotecki BJ. Fernando DP. Haight AR. Lukin KA. Org. Lett.  2009,  11:  947 
    Google Scholar
  • 1u Wang F. Liu X. Cui X. Xiong Y. Zhou X. Feng X. Chem. Eur. J.  2009,  15:  589 
    Google Scholar
  • 1v Reis Ö. Eymur S. Reis B. Demir AS. Chem. Commun.  2009,  1088 
    Google Scholar
  • For reviews, see:
  • 2a Taylor MS. Jacobsen EN. Angew. Chem. Int. Ed.  2006,  45:  1520 
    Google Scholar
  • 2b Connon SJ. Chem. Commun.  2008,  2499 
    Google Scholar
  • 2c Zhang Z. Schreiner PR. Chem. Soc. Rev.  2009,  38:  1187 
    Google Scholar
  • 3a Batt DG. Houghton GC. Roderick J. Santella JB. Wacker DA. Welch PK. Orlovsky YI. Wadman EA. Trzaskos JM. Davies P. Decicco CP. Carter PH. Bioorg. Med. Chem. Lett.  2004,  15:  787 
    Google Scholar
  • 3b Vidaluc J.-L, and Bigg D. inventors; USPTO  5288758. 
  • 3c Rautenberg W, Harting J, Greiner H, Bartoszyk G, Böttcher H, Van Amsterdam C, and Matzen L. inventors; EP  1140898. 
  • 3d Kaplan AP, and Gupta V. inventors; USPTO  20080306048. 
  • 4a Bankston D. Dumas J. Natero R. Riedl B. Monahan M.-K. Sibley R. Org. Process Res. Dev.  2002,  6:  777 
    Google Scholar
  • 4b Clark JW. Eder JP. Ryan D. Lathia C. Lenz H.-J. Clin. Cancer Res.  2005,  11:  5472 
    Google Scholar
  • 4c Wilhelm S. Carter C. Lynch M. Lowinger T. Dumas J. Smith RA. Schwartz B. Simantov R. Kelley S. Nat. Rev. Drug Discovery  2006,  5:  835 
    Google Scholar
  • 4d Murphy DA. Makonnen S. Lassoued W. Feldman MD. Carter C. Lee WMF. Am. J. Pathol.  2006,  169:  1875 
    Google Scholar
  • 4e Steinbild S. Mross K. Frost A. Morant R. Gillessen S. Dittrich C. Strumberg D. Hochhaus A. Hanauske A.-R. Edler L. Burkholder I. Scheulen M. Br. J. Cancer  2007,  97:  1480 
    Google Scholar
  • 5a Fabian MA. Biggs WH. Treiber DK. Atteridge CE. Azimioara MD. Benedetti MG. Carter TA. Ciceri P. Edeen PT. Floyd M. Ford JM. Galvin M. Gerlach JL. Grotzfeld RM. Herrgard S. Insko DE. Insko MA. Lai AG. Lélias J.-M. Mehta SA. Milanov ZV. Velasco AM. Wodicka LM. Patel HK. Zarrinkar PP. Lockhart DJ. Nat. Biotechnol.  2005,  23:  329 
    Google Scholar
  • 5b Quesada AR. Munoz-Chápuli R. Medina MA. Med. Res. Rev.  2006,  26:  483 
    Google Scholar
  • 5c Liao JJ.-L. J. Med. Chem.  2007,  50:  409 
    Google Scholar
  • 6a Jackson RC. Weber G. Nature  1975,  256:  331 
    Google Scholar
  • 6b Markland W. McQuaid TJ. Jain J. Kwong AD. Antimicrob. Agents Chemother.  2000,  44:  859 
    Google Scholar
  • 6c Gu HH. Iwanowicz EJ. Guo J. Watterson SH. Shen Z. Pitts WJ. Dhar TGM. Fleener CA. Rouleau K. Sherbina NZ. Witmer M. Tredup J. Hollenbaugh D. Bioorg. Med. Chem. Lett.  2002,  12:  1323 
    Google Scholar
  • 7a Rudzevich Y. Cao Y. Rudzevich V. Böhmer V. Chem. Eur. J.  2008,  14:  3346 
    Google Scholar
  • 7b Chauhan SMS. Bisht T. Garg B. Tetrahedron Lett.  2008,  49:  6646 
    Google Scholar
  • 7c dos Santos CMG. McCabe T. Watson GW. Kruger PE. Gunnlaugsson T. J. Org. Chem.  2008,  73:  9235 
    Google Scholar
  • 7d Ye S. Ding Q. Wang Z. Zhou H. Wu J. Org. Biomol. Chem.  2008,  6:  4406 
    Google Scholar
  • 7e Cui Y.-M. Yasutomi E. Otani Y. Yoshinaga T. Ido K. Sawada K. Ohwada T. Bioorg. Med. Chem. Lett.  2008,  18:  5201 
    Google Scholar
  • 7f Clayden J. Lemiègre L. Morris GA. Pickworth M. Snape PJ. Jones LH. J. Am. Chem. Soc.  2008,  130:  15193 
    Google Scholar
  • Reviews:
  • 8a Stang PJ. Zhdankin VV. Chem. Rev.  2008,  108:  5299 
    Google Scholar
  • 8b Zhdankin VV. ARKIVOC  2009,  (i):  1 
    Google Scholar
  • 9a Loudon GM. Radhakrishna AS. Almond MR. Blodgett JK. Boutin RH. J. Org. Chem.  1984,  49:  4272 
    Google Scholar
  • 9b Lazbin IM. Koser GF. J. Org. Chem.  1986,  51:  2669 
    Google Scholar
  • 9c Vasudevan A. Koser GF. J. Org. Chem.  1988,  53:  5158 
    Google Scholar
  • 11 See also: Moriarty RM. Chany CJ. Vaid RK. Prakash O. Tuladhar SM. J. Org. Chem.  1993,  58:  2478 
    CrossrefGoogle Scholar
  • 12 Irschik H. Gerth K. Höfle G. Kohl W. Reichenbach H. J. Antibiot.  1983,  36:  1651 
    Google Scholar
  • 13 Irschik H. Jansen R. Höfle G. Gerth K. Reichenbach H. J. Antibiot.  1985,  38:  145 
    Google Scholar
10

Representative Procedure (Table 1, Entry 1): A solution of benzamide (121 mg, 1.00 mmol), PhI(OAc)2 (DAIB; 419 mg, 1.30 mmol) and H2O (54 µL, 3.00 mmol) in CH2Cl2 (10 mL) was stirred at ambient temperature for 16 h. The resulting solution was stirred at 40 ˚C for 1 h, then the solution was concentrated under vacuum and the remaining residue was purified by column chromatography on silica gel (hexane-EtOAc, 3:1) to yield the corresponding urea as a colorless solid (52.4 mg, 49%).