Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000084.xml
Synthesis 2014; 46(14): 1886-1900
DOI: 10.1055/s-0033-1339127
DOI: 10.1055/s-0033-1339127
special topic
Formation of Imidazolidine-benzothiazole–Copper(II) Complexes via a Copper-Mediated Room-Temperature C–H Activation of Imidazolidinecarbothioamides
Further Information
Publication History
Received: 12 April 2014
Accepted after revision: 05 May 2014
Publication Date:
22 May 2014 (online)
Abstract
Treatment of N-aryl-2-(arylimino)imidazolidine-1-carbothioamide, and unsymmetrical thiourea, with copper(II) chloride or bromide results in aryl sp2 C–H activation (C–S bond formation) at room temperature to form a 2-[2-(arylimino)imidazolidin-1-yl]benzothiazole with concurrent formation of a 2-imidazolidin-1-ylbenzothiazole–copper(II) complex. In all the complexes the imine and benzothiazole nitrogens are s-cis, whereas in the isolated ligands they are s-trans oriented. Due to the presence of a suitable H-donor site and halogen atoms in the metal complexes and ligands, several supramolecular assemblies exist through H-bonding interactions; classical N–H···X–Cu (F, Cl, Br), nonclassical C–H···X–Cu H–bonds, and halogen···π and halogen···halogen interactions.
Key words
copper catalysis - imidazolidinecarbothioamide - C–H activation - aminothiazole - halogen bonding - supramolecular assemblySupporting Information
- for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000084. Included are X-ray crystallographic data (CIF files) of all the synthesized compounds, spectral data of all compounds, and copies of 1H, 13C NMR and MS spectra of products associated with this article.
- Supporting Information
-
References
- 1a Jordan AD, Luo C, Reitz AB. J. Org. Chem. 2003; 68: 8693
- 1b Le Z.-G, Xu J.-P, Rao H.-Y, Ying M. J. Heterocycl. Chem. 2006; 43: 1123
- 2a Yella R, Murru S, Ali AR, Patel BK. Org. Biomol. Chem. 2010; 8: 3389
- 2b Yella R, Patel BK. J. Comb. Chem. 2010; 12: 754
- 3a Sahoo SK, Banerjee A, Chakraborty S, Patel BK. ACS Catal. 2012; 2: 544
- 3b Rout SK, Guin S, Nath J, Patel BK. Green Chem. 2012; 14: 2491
- 3c Khatun N, Jamir L, Ganesh M, Patel BK. RSC Adv. 2012; 2: 11557
- 4a Sahoo SK, Khatun N, Gogoi A, Deb A, Patel BK. RSC Adv. 2013; 3: 438
- 4b Sahoo SK, Khatun N, Jena HS, Patel BK. Inorg. Chem. 2012; 51: 10800
- 5 Ghosh H, Yella R, Nath J, Patel BK. Eur. J. Org. Chem. 2008; 6189
-
6a Brasche G, Buchwald SL. Angew. Chem. Int. Ed. 2008; 47: 1932
-
6b Ueda S, Nagasawa H. Angew. Chem. Int. Ed. 2008; 47: 6411
- 6c Ueda S, Nagasawa H. J. Org. Chem. 2009; 74: 4272
- 7 Casitas A, King AE, Parella T, Costas M, Stahl SS, Ribas X. Chem. Sci. 2010; 1: 326
-
8 Phipps RJ, Grimster NP, Gaunt MJ. J. Am. Chem. Soc. 2008; 130: 8172
- 9a Halogen Bonding: Fundamentals and Applications, In Structure and Bonding . Vol. 126. Metrangolo P, Resnati G. Springer; Berlin: 2008
- 9b Metrangolo P, Neukirch H, Pilati T, Resnati G. Acc. Chem. Res. 2005; 38: 386
- 9c Brammer L, Minguez Espallargas G, Libri S. CrystEngComm 2008; 10: 1712
- 9d Zordan F, Brammer L, Sherwood P. J. Am. Chem. Soc. 2005; 127: 5979
- 9e Smart P, Bejarano-Villafuerte A, Brammer L. CrystEngComm 2013; 15: 3160
- 9f Smart P, Bejarano-Villafuerte A, Hendry RM, Brammer L. CrystEngComm 2013; 15: 3151
- 10a Legon AC In Halogen Bonding: Fundamentals and Applications, In Structure and Bonding . Vol. 126. Metrangolo P, Resnati G. Springer; Berlin: 2008: 17
- 10b Metrangelo P, Meyer F, Pilati T, Resnati G, Terraneo G. Angew. Chem. Int. Ed. 2008; 47: 6114
- 11a Desijaru GR. Nature (London) 2001; 413: 397
- 11b Metrangolo P, Resnati G. Chem. Eur. J. 2001; 7: 2511
- 11c Bosch E, Barnes CL. Cryst. Growth Des. 2002; 2: 299
- 11d Braga D, Brammer L, Champness N. CrystEngComm 2005; 7: 1
- 11e Aakeröy CB, Chopade PD, Desper J. Cryst. Growth Des. 2011; 11: 5333
- 12a Sanchez C, Belleville P, Popall M, Nicole L. Chem. Soc. Rev. 2011; 40: 696
- 12b Pardo R, Zayat M, Levy D. Chem. Soc. Rev. 2011; 40: 672
- 13a Awwadi FF, Willett RD, Peterson KA, Twamley B. Chem. Eur. J. 2006; 12: 8952
- 13b Desiraju GR, Parthasarathy R. J. Am. Chem. Soc. 1989; 111: 8725
- 14a Takeuchi T, Minato Y, Takase M, Shinmori H. Tetrahedron Lett. 2005; 46: 9025
- 14b Burton DD, Fontana F, Metrangolo P, Pilati T, Resnati G. Tetrahedron Lett. 2003; 44: 645
- 14c Liantonio R, Metrangolo P, Pilati T, Resnati G, Stevenazzi A. Cryst. Growth Des. 2003; 3: 799
- 15a Grotjahn DB, Van S, Combs D, Lev DA, Schneider C, Incarvito CD, Lam K.-C, Rossi G, Rheingold AL, Rideout M, Meyer C, Hernandez G, Mejorado L. Inorg. Chem. 2003; 42: 3347
- 15b Niu W, Smith MD, Lavigne JJ. Cryst. Growth Des. 2006; 6: 1274
- 15c Varughese S, Draper SM. Cryst. Growth Des. 2010; 10: 2571
- 15d Habata Y, Noto K, Osaka F. Inorg. Chem. 2007; 46: 6529
- 15e Jena HS. RSC Adv. 2014; 4: 3028
- 15f Notash B, Safari N, Khavasi HR. Inorg. Chem. 2010; 49: 11415
- 15g Notash B, Safari N, Khavasi HR. CrystEngComm 2012; 14: 6788
- 16 Yang L, Powell DR, Houser RP. Dalton Trans. 2007; 955
- 17 Sengupta S, Goswami A, Ganguly S, Bala S, Bhunia MK, Mondal R. CrystEngComm 2011; 13: 6136
- 18 Tero T.-R, Salorinne K, Nissinen M. CrystEngComm 2012; 14: 7360
- 19 Salonen LM, Ellermann M, Diederich F. Angew. Chem. Int. Ed. 2011; 50: 4808
- 20a Nath J, Ghosh H, Yella R, Patel BK. Eur. J. Org. Chem. 2009; 1849
- 20b Nath J, Patel BK, Jamir L, Sinha UB, Satyanarayanan KV. V. V. Green Chem. 2009; 11: 1503
- 20c Yella R, Ghosh H, Murru S, Sahoo SK, Patel BK. Synth. Commun. 2010; 40: 2083
- 21 Saint, Smart XPREP . Siemens Analytical X-ray Instruments Inc; Madison (WI, USA): 1995
- 22 Sheldrick GM. SADABS: Software for Empirical Absorption Correction . University of Göttingen; Germany: 1999
- 23 Sheldrick GM. SHELXS-97. University of Göttingen; Germany: 1997
- 24 Sheldrick GM. SHELXL-97, Program for Crystal Structure Refinement. University of Göttingen; Germany: 1997
- 25 Farrugia LJ. J. Appl. Crystallogr. 1997; 30: 565
- 26 Mercury 1.3, Supplied with Cambridge Structural Database. CCDC; Cambridge (UK): 2003