RSS-Feed abonnieren
Bitte kopieren Sie die angezeigte URL und fügen sie dann in Ihren RSS-Reader ein.
https://www.thieme-connect.de/rss/thieme/de/10.1055-s-00000084.xml
Synthesis 2013; 45(3): 347-354
DOI: 10.1055/s-0032-1316833
DOI: 10.1055/s-0032-1316833
paper
Synthesis, Characterization, and Reactivity of N-Acyl Chloroformamidines: Useful Building Blocks for the Construction of N-Acyl-Substituted 1,1-Diaminoethylenes, Amidines, Ureas, and Thioureas
Weitere Informationen
Publikationsverlauf
Received: 23. Oktober 2012
Accepted after revision: 03. Dezember 2012
Publikationsdatum:
12. Dezember 2012 (online)
Abstract
The systematic synthesis of a series of N-acyl chloroformamidines is achieved by reaction of carbodiimides with acid chlorides; the structure of an N-acyl chloroformamidine was confirmed by X-ray diffraction. The reactivity of N-acyl chloroformamidines towards diethyl malonate, phenylethynyllithium, pentane-2,4-dione, methyl acetoacetate, water, 1,3-dimethylurea, 1,3-dimethylthiourea, and sodium hydrosulfide, resulted in unique protocols for the synthesis of N-acyl-substituted 1,1-diaminoethylenes, amidines, ureas, and thioureas, respectively. These results show that N-acyl chloroformamidines have a good ability to accept nucleophilic attack for the construction of useful N-containing compounds.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synthesis. Included are spectroscopic data (1H and 13C NMR spectra for new compounds and X-ray data for compound 3a).
- Supporting Information
-
References
- 1a Suzuki T, Zhang W.-X, Nishiura M, Hou Z. J. Synth. Org. Chem., Jpn. 2009; 67: 451
- 1b Shen H, Xie Z. J. Organomet. Chem. 2009; 694: 1652
- 1c Zhang W.-X, Hou Z. Org. Biomol. Chem. 2008; 6: 1720
- 1d Edelmann FT. Adv. Organomet. Chem. 2008; 57: 183
- 1e Coles MP. Dalton Trans. 2006; 985
- 1f Bailey P, Pace JS. Coord. Chem. Rev. 2001; 214: 91
- 1g Barker J, Kilner M. Coord. Chem. Rev. 1994; 133: 219
- 1h Mikolajczyk M, Kielbasinski P. Tetrahedron 1981; 37: 233
- 1i Williams A, Ibrahim IT. Chem. Rev. 1981; 81: 589
- 2a Qiu G, He Y, Wu J. Chem. Commun. 2012; 48: 3836
- 2b Shen H, Wang Y, Xie Z. Org. Lett. 2011; 13: 4562
- 2c Alajarin M, Bonillo B, Ortin M.-M, Orenes R.-A, Vidal A. Org. Biomol. Chem. 2011; 9: 6741
- 2d Alajarin M, Bonillo B, Ortin M.-M, Sanchez-Andrada P, Vidal A. Eur. J. Org. Chem. 2011; 1896
- 2e Wang F, Cai S, Liao Q, Xi C. J. Org. Chem. 2011; 76: 3174
- 2f Alizadeh A, Zohreh N, Oskueyan G, Zhu L.-G. Synlett 2011; 2491
- 2g Zeng F, Alper H. Org. Lett. 2010; 12: 1188
- 2h Zeng F, Alper H. Org. Lett. 2010; 12: 3642
- 2i Saito T, Furukawa N, Otani T. Org. Biomol. Chem. 2010; 8: 1126
- 2j Alajarin M, Bonillo B, Marin-Luna M, Sanchez-Andrada P, Vidal A. Eur. J. Org. Chem. 2010; 694
- 2k Shen G, Bao W. Adv. Synth. Catal. 2010; 352: 981
- 2l Alajarin M, Bonillo B, Ortin M.-M, Sanchez-Andrada P, Vidal A, Orenes R.-A. Org. Biomol. Chem. 2010; 8: 4690
- 2m Lv X, Bao W. J. Org. Chem. 2009; 74: 5618
- 2n Alajarin M, Bonillo B, Marin-Luna M, Vidal A, Orenes R.-A. J. Org. Chem. 2009; 74: 3558
- 2o Yu RT, Rovis T. J. Am. Chem. Soc. 2008; 130: 3262
- 2p Volonterio A, Zanda M. Org. Lett. 2007; 9: 841
- 2q Saito T, Sugizaki K, Otani T, Suyama T. Org. Lett. 2007; 9: 1239
- 2r Xu X, Cheng D, Li J, Guo H, Yan J. Org. Lett. 2007; 9: 1585
- 2s Li H, Petersen JL, Wang KK. J. Org. Chem. 2003; 68: 5512
- 2t Schmittel M, Rodríguez D, Steffen J.-P. Angew. Chem. Int. Ed. 2000; 39: 2152
- 3a Seyfried MS, Lauber BS, Luedtke NW. Org. Lett. 2010; 12: 104
- 3b Alonso-Moreno C, Carrillo-Hermosilla F, Garcés A, Otero A, López-Solera I, Rodríguez AM, Antiñolo A. Organometallics 2010; 29: 2789
- 3c Barrett AG. M, Crimmin MR, Hill MS, Hitchcock PB, Lomas SL, Mahona MF, Procopioud PA. Dalton Trans. 2010; 39: 7393
- 3d Zhu X, Du Z, Xu F, Shen Q. J. Org. Chem. 2009; 74: 6347
- 3e Zhang W.-X, Nishiura M, Mashiko T, Hou Z. Chem. Eur. J. 2008; 14: 2167
- 3f Crimmin MR, Barrett AG. M, Hill MS, Hitchcock PB, Procopiou PA. Organometallics 2008; 27: 497
- 3g Du Z, Li W, Zhu X, Xu F, Shen Q. J. Org. Chem. 2008; 73: 8966
- 3h Zhang W.-X, Nishiura M, Hou Z. Chem. Eur. J. 2007; 13: 4037
- 3i Li Q, Wang S, Zhou S, Yang G, Zhu X, Liu Y. J. Org. Chem. 2007; 72: 6763
- 3j Ong T.-G, O’Brien JS, Korobkov I, Richeson DS. Organometallics 2006; 25: 4728
- 3k Shen H, Chan H.-S, Xie Z. Organometallics 2006; 25: 5515
- 3l Montilla F, del Río D, Pastor A, Galindo A. Organometallics 2006; 25: 4996
- 3m Zhang W.-X, Nishiura M, Hou Z. Chem. Commun. 2006; 3812
- 3n Zhang W.-X, Nishiura M, Hou Z. Synlett 2006; 1213
- 3o Zhang W.-X, Nishiura M, Hou Z. J. Am. Chem. Soc. 2005; 127: 16788
- 3p Ong T.-G, Yap GP. A, Richeson DS. J. Am. Chem. Soc. 2003; 125: 8100
- 4a Wang Y, Chi Y, Zhang W.-X, Xi Z. J. Am. Chem. Soc. 2012; 134: 2926
- 4b Wentrup C. Acc. Chem. Res. 2011; 44: 393
- 4c Kvaskoff D, Vosswinkel M, Wentrup C. J. Am. Chem. Soc. 2011; 133: 5413
- 4d Wang Z, Wang Y, Zhang W.-X, Hou Z, Xi Z. J. Am. Chem. Soc. 2009; 131: 15108
- 5a Kuninobu Y, Uesugi T, Kawata A, Takai K. Angew. Chem. Int. Ed. 2011; 50: 10406
- 5b Ong T.-G, Yap GP. A, Richeson DS. Chem. Commun. 2003; 2612
- 5c Zuckerman RL, Bergman RG. Organometallics 2000; 19: 4795
- 6a Brady WT, Owens RA. J. Org. Chem. 1977; 42: 3220
- 6b Hartke K. Chem. Ber. 1966; 99: 3163
- 6c Hartke K, Palou E. Chem. Ber. 1966; 99: 3155
- 7 Xu X, Gao J, Cheng D, Li J, Qiang G, Guo H. Adv. Synth. Catal. 2008; 350: 61
- 8 Wang Y, Zhang W.-X, Wang Z, Xi Z. Angew. Chem. Int. Ed. 2011; 50: 8122
- 9 Zhao F, Wang Y, Zhang W.-X, Xi Z. Org. Biomol. Chem. 2012; 10: 6266
- 10a Klotz U, Gonlieb W, Keohane PP, Dammann HG. J. Clin. Pharmacol. 1987; 27: 210
- 10b Daly MJ, Price BJ. Prog. Med. Chem. 1983; 20: 337
- 10c Collins JL, Shearer BG, Oplinger JA, Lee S, Garvey EP, Salter M, Dufry C, Burnette TC, Furtine ES. J. Med. Chem. 1998; 41: 2858
- 10d Thioureas. In The Pesticide Manual . 7th ed. Worting CR, Walker SB. The British Crop Protection Council; London: 1983
- 10e Ramadus K, Suresh G, Janarthanan N, Masilamani S. Pestic. Sci. 1998; 52: 145
- 11a Li D, Wang Y, Zhang W.-X, Zhang S, Guang J, Xi Z. Organometallics 2011; 30: 5278
- 11b Li D, Guang J, Zhang W.-X, Wang Y, Xi Z. Org. Biomol. Chem. 2010; 8: 1816
- 11c Zhang W.-X, Li D, Wang Z, Xi Z. Organometallics 2009; 28: 882
- 12a Liptrot D, Alcaraz L, Roberts B. Adv. Synth. Catal. 2010; 352: 2183
- 12b Maki T, Ishihara K, Yamamoto H. Synlett 2004; 1355
- 12c Seiller B, Hins D, Bruneau C, Dixneuf PH. Tetrahedron 1995; 51: 10901
- 12d Kutschy P, Dzurilla M, Ficeri V, Koscik D. Collect. Czech. Chem. Commun. 1993; 58: 575
- 12e Kishikawa K, Horie K, Yamamoto M, Kohmoto S, Yamada K. Chem. Lett. 1990; 1009
- 12f Deng M.-Z, Caubere P, Senet JP, Lecolier S. Tetrahedron 1988; 44: 6079
- 12g Ulrich H, Tucker B, Richter R. J. Org. Chem. 1978; 43: 1544
- 12h Speziale AJ, Smith LR. J. Org. Chem. 1962; 27: 3742
- 12i Stoughton RW. J. Org. Chem. 1938; 2: 514
Selected reviews of carbodiimide chemistry:
Selected examples of cycloaddition of carbodiimides:
Selected examples of addition of nucleophiles to carbodiimides:
For examples of rearrangement of carbodiimides, see:
For examples of carbodiimide metathesis:
1,1-Diaminoethene:
Amidines:
Ureas:
For the synthesis of N-acylureas, see: