Dramatic Solvent Effect in the One-Pot Synthesis of Substituted Ureas Directly from Primary Alcohols Using the Combined Reagent of Iodobenzene Dichloride and Sodium Azide in Ethyl Acetate

Abstract

A highly efficient and practical method for the synthesis of substituted ureas directly from various primary alcohols and amines has been developed. This method is based on the finding that the use of ethyl acetate as the solvent can result in an improved efficiency of the transformation of various primary alcohols to their corresponding carbamoyl azides with the combined reagent of iodobenzene dichloride (PhICl₂) and sodium azide.

Key words

alcohols - amines - oxidation - iodobenzene dichloride - hypervalent iodine

• References


For some reviews on substituted ureas, see:
• 1a Vishnyakova TP, Golubeva IA, Glebova EV. Russ. Chem. Rev. (Engl. Transl.) 1985; 54: 249
• 1b Matsuda K. Med. Res. Rev. 1994; 14: 271
• 1c Amendola V, Fabbrizzi L, Mosca L. Chem. Soc. Rev. 2010; 39: 3889
• 1d Bigi F, Maggi R, Sartori G. Green Chem. 2000; 2: 140
• 1e Volz N, Clayden J. Angew. Chem. Int. Ed. 2011; 50: 12148
• 1f Gallou I. Org. Prep. Proced. Int. 2007; 39: 355

For selected examples of urea-based bifunctional organocatalysts in organic synthesis, see:
• 2a Lang K, Park J, Hong S. Angew. Chem. Int. Ed. 2012; 51: 1620
• 2b Gu Q, You S.-L. Org. Lett. 2011; 13: 5192
• 2c So SS, Auvil TJ, Garza VJ, Mattson AE. Org. Lett. 2012; 14: 444

For selected examples of substituted ureas as intermediates in organic synthesis, see:
• 3a Cochran BM, Michael FE. Org. Lett. 2008; 10: 5039
• 3b Wang L, Liu S, Li Z, Yu Y. Org. Lett. 2011; 13: 6137
• 3c LaLonde RL, Brenzovich WE. Jr, Benitez D, Tkatchouk E, Kelley K, Goddard WA, Toste FD. Chem. Sci. 2010; 1: 226
• 3d Clayden J, Dufour J, Grainger DM, Helliwell M. J. Am. Chem. Soc. 2007; 129: 7488
• 4 Yin X.-L, Jiang L, Song N.-H, Yang H. J. Agric. Food Chem. 2008; 56: 4825
• 5 Kim JG, Takami Y, Mizugami T, Beppu K, Fukuda T, Kataoka I. Sci. Hortic. 2006; 110: 219
• 6 Deeks SG, Smith M, Holodniy M, Kahn JO. J. Am. Med. Assoc. 1997; 277: 145
• 7 Millan DS, Bunnage ME, Burrows JL, Butcher KJ, Dodd PG, Evans TJ, Fairman DA, Hughes SJ, Kilty IC, Lemaitre A, Lewthwaite RA, Mahnke A, Mathias JP, Philip J, Smith RT, Stefaniak MH, Yeadon M, Phillips C. J. Med. Chem. 2011; 54: 7797
• 8 Babad H, Zeiler AG. Chem. Rev. 1973; 73: 75
• 9a Ozaki S. Chem. Rev. 1972; 72: 457
• 9b Lefranc J, Tetlow DJ, Donnard M, Minassi A, Gálvez E, Clayden J. Org. Lett. 2011; 13: 296

For selected examples of the preparation of ureas from phosgene substitutes, see:
• 10a Gallou I, Eriksson M, Zeng X, Senanayake C, Farina V. J. Org. Chem. 2005; 70: 6960
• 10b Azad S, Kumamoto K, Uegaki K, Ichikawa Y, Kotsuki H. Tetrahedron Lett. 2006; 47: 587
• 10c Artuso E, Degani I, Fochi R, Magistris C. Synthesis 2007; 3497
• 10d Jagtap SR, Patil YP, Panda AG, Bhanage BM. Synth. Commun. 2009; 39: 2093
• 10e Ballini R, Fiorini D, Maggi R, Righi P, Sartoriband G, Sartorio R. Green Chem. 2003; 5: 396
• 10f Batey RA, Santhakumar V, Yoshina-Ishii C, Taylor SD. Tetrahedron Lett. 1998; 39: 6267
• 10g Katritzky AR, Pleynet DP. M, Yang B. J. Org. Chem. 1997; 62: 4155
• 10h Majer P, Randad RS. J. Org. Chem. 1994; 59: 1937
• 10i Leung M, Lai J.-L, Lau K.-H, Yu H, Hsiao H.-J. J. Org. Chem. 1996; 61: 4175
• 11 Díaz DJ, Darko AK, McElwee-White L. Eur. J. Org. Chem. 2007; 4453
• 12a Wu C, Cheng H, Liu R, Wang Q, Hao Y, Yu Y, Zhao F. Green Chem. 2010; 12: 1811
• 12b Jiang T, Ma X, Zhou Y, Liang S, Zhang J, Han B. Green Chem. 2008; 10: 465
• 12c Ion A, Parvulescu V, Jacobs P, Vos DD. Green Chem. 2007; 9: 158
• 13a Willgerodt C. J. Prakt. Chem. 1886; 33: 154
• 13b Banks DF. Chem. Rev. 1966; 66: 243
• 13c Stang PJ, Zhdankin VV. Chem. Rev. 1996; 96: 1123
• 13d Stang PJ, Zhdankin VV. Chem. Rev. 2002; 102: 2523
• 13e Zhdankin VV, Stang PJ. Chem. Rev. 2008; 108: 5299
• 14 Li X.-Q, Wang W.-K, Zhang C. Adv. Synth. Catal. 2009; 351: 2342
• 15a Lieber E, Minnis RL. Jr, Rao CN. R. Chem. Rev. 1965; 65: 377
• 15b Marinescu L, Thinggaard J, Thomsen IB, Bols M. J. Org. Chem. 2003; 68: 9453
• 16 PhICl₂ was recrystallized from chloroform.
• 17 Khan KM, Saeed S, Ali M, Gohar M, Zahid J, Khan A, Perveen S, Choudhary MI. Bioorg. Med. Chem. 2009; 17: 2447
• 18 Li X.-Q, Wang W.-K, Han Y.-X, Zhang C. Adv. Synth. Catal. 2010; 352: 2588
• 19 Magnus P, Lacour J. J. Am. Chem. Soc. 1992; 114: 767
• 20 Zhao X.-F, Zhang C. Synthesis 2007; 551
• 21 Li X.-Q, Zhao X.-F, Zhang C. Synthesis 2008; 2589
• 22 Brandt JC, Wirth T. Beilstein J. Org. Chem. 2009; 5: No. 30 ; doi: 10.3762/bjoc.5.30
• 23 Kotecki BJ, Fernando DP, Haight AR, Lukin KA. Org. Lett. 2009; 11: 947
• 24 Mizuno T, Mihara M, Nakai T, Iwai T, Ito T. Synthesis 2007; 3135