Synlett, Inhaltsverzeichnis Synlett 2014; 25(14): 2044-2048DOI: 10.1055/s-0034-1378376 letter © Georg Thieme Verlag Stuttgart · New York Zinc Chloride Catalyzed Ring Opening of N-Arylsulfonyl Aziridines by Thioamides: A New Approach to the Synthesis of Amidines Khadijeh Hajibabaei Department of Chemistry, University of Isfahan, 81746-73441 Isfahan, Iran Fax: +98(311)6689732 eMail: h.zali@chem.ui.ac.ir , Hassan Zali-Boeini* Department of Chemistry, University of Isfahan, 81746-73441 Isfahan, Iran Fax: +98(311)6689732 eMail: h.zali@chem.ui.ac.ir › Institutsangaben Artikel empfehlen Abstract Artikel einzeln kaufen Alle Artikel dieser Rubrik Abstract The first zinc chloride catalyzed ring opening of N-arylsulfonyl aziridines by thioamides is described. Various thioamides were reacted with N-arylsulfonyl aziridines in the presence of a catalytic amount of dry zinc chloride to provide the corresponding N-arylsulfonyl amidine derivatives with good to excellent yields. Key words Key wordsamides - Lewis acids - nitrogen - homogeneous catalysis - sulfur Volltext Referenzen References and Notes 1a Sienkiewich P, Bielawski K, Bielawska A, Palka J. Environ. Toxicol. Pharmacol. 2005; 20: 118 1b Greenhill JV, Lue P. Prog. Med. Chem. 1993; 30: 203 2a The Chemistry of Amidines and Imidates . Patai S, Rappoport Z. Wiley; New York: 1991 2b Lee MY, Kim MH, Kim J, Kim SH, Kim BT, Jeong IH, Chang S, Kim SH, Chang SY. Bioorg. Med. Chem. Lett. 2010; 20: 541 3 Chen S, Xu Y, Wan X. Org. Lett. 2011; 13: 6152 4a Bae I, Han H, Chang S. J. Am. Chem. Soc. 2005; 127: 2038 4b Yoo EJ, Bae I, Cho SH, Han H, Chang S. Org. Lett. 2006; 8: 1347 4c Chang S, Lee MJ, Jung DY, Yoo EJ, Cho SH, Han SK. J. Am. Soc. Chem. 2006; 128: 12366 4d Kim JY, Kim SH, Chang S. Tetrahedron Lett. 2008; 49: 1745 4e Yoo EJ, Chang S. Org. Lett. 2008; 10: 1163 5a Whiting M, Fokin VV. Angew. Chem. Int. Ed. 2006; 45: 3157 5b Yoo EJ, Ahlquist M, Bae I, Sharpless KB, Fokin VV, Chang S. J. Org. Chem. 2008; 73: 5520 6a Shang Y, He X, Hu J, Wu J, Zhang M, Yu S, Zhang Q. Adv. Synth. Catal. 2009; 351: 2709 6b Mandal S, Gauniyal HM, Pramanik K, Mukhopadhyay B. J. Org. Chem. 2007; 72: 9753 6c Xu X, Cheng D, Li J, Guo H, Yan J. Org. Lett. 2007; 9: 1585 7a Wang S, Wang Z, Zheng X. Chem. Commun. 2009; 7372 7b Xu X, Li X, Ma L, Ye N, Weng B. J. Am. Chem. Soc. 2008; 130: 14048 7c Liu N, Tang BY, Chen Y, He L. Eur. J. Org. Chem. 2009; 2059 7d Xu X, Ge Z, Cheng D, Ma L, Lu C, Zhang Q, Yao N, Li X. Org. Lett. 2010; 12: 897 7e Zhang L, Su JH, Wang S, Wan C, Zha Z, Du J, Wang Z. Chem. Commun. 2011; 47: 5488 8 Gao T, Zhao M, Meng X, Li C, Chen B. Synlett 2011; 1281 9a Jacobsen CB, Jørgensen KA. Org. Biomol. Chem. 2008; 6: 3467 9b Nenajdenko VG, Karpov AS, Balenkova ES. Tetrahedron: Asymmetry 2001; 12: 2517 10a Hu XE. Tetrahedron 2004; 60: 2701 10b D’hooghe M, Van Speybroeck V, Waroquier M, De Kimpe N. Chem. Commun. 2006; 1554 10c Lu P. Tetrahedron 2010; 66: 2549 11a Wu J, Sun X, Sum W. Org. Biomol. Chem. 2006; 4: 4231 11b Ghorai MG, Das K, Shukla D. J. Org. Chem. 2007; 72: 5859 11c Stanković S, D’hooghe M, Catak S, Eum H, Waroquier M, Speybroeck VV, Kimpe ND, Ha H. Chem. Soc. Rev. 2012; 41: 643 11d Chandrasekhar S, Narsihmulu C, Shameem Sultana S. Tetrahedron Lett. 2002; 43: 7361 12 Alagiri K, Prabhu KR. Chem. Eur. J. 2011; 17: 6922 13 Wu JY, Luo ZB, Dai LX, Hou XL. J. Org. Chem. 2008; 73: 9137 14 Gopinath P, Debasree C, Vidyarini RS, Chandrasekaran S. Tetrahedron 2010; 66: 7001 15 Jagodzinski TS. Chem. Rev. 2003; 103: 197 16 Zali-Boeini H, Mobin M. Synlett 2010; 2861 17a Zali-Boeini H, Eshghi Kashan M. Green Chem. 2009; 11: 1987 17b Zali-Boeini H, Zali A. Synth. Commun. 2011; 41: 2421 17c Zali-Boeini H, Khajeh A. Bull. Korean Chem. Soc. 2011; 32: 1201 18 Gao T, Zhao M, Meng X, Li C, Chen B. Synlett 2011; 1281 19 Zbruyev OI, Stiasni N, Kappe CO. J. Comb. Chem. 2003; 5: 145 20 Daisuke K, Satoshi M, Mitsuo K. J. Chem. Soc., Perkin Trans. 1 2001; 3186 21 Complete experimental procedures and relevant 1H NMR and 13C NMR spectra and elemental microanalysis for new compounds are available in the Supporting Information. Typical Procedure for the Synthesis of N-Arylsulfonyl Amidine 3a A suspension of anhydrous ZnCl2 (3.2 mg, 2 mol%) in anhydrous CH2Cl2 (2.0 mL) was refluxed for 5 min, a solution of 2-phenyl-1-tosylaziridine (2a, 328 mg, 1.2 mmol) in anhydrous CH2Cl2 (1.0 mL) was added slowly, and the mixture was stirred at 40 °C for a further 5 min. Morpholino(phenyl) methanethione (1a, 207 mg, 1 mmol) was then added, and the mixture was stirred at the same temperature for 2 h. The reaction mixture was then triturated with H2O (5 mL) to remove ZnCl2 and extracted with CH2Cl2 (3 × 5 mL). The combined organic layers were dried over MgSO4, filtered, and concentrated under vacuum. Finally, the residue was subjected to column chromatog-raphy on silica gel eluting with PE–EtOAc (1:1) to furnish amidine 3a as a white solid (314 mg, 91%). Zusatzmaterial Zusatzmaterial Supporting Information
