Palladium-Catalyzed One-Pot Synthesis of N-Sulfonyl, N-Phosphoryl, and N-Acyl Guanidines

Abstract

An efficient palladium-catalyzed cascade reaction of azides with isonitrile and amines is presented; it offers an alternative facile approach toward N-sulfonyl-, N-phosphoryl-, and N-acyl-functionalized guanidines in excellent yield. These series of substituted guanidines exhibit potential biological and pharmacological activities. In addition, the less reactive intermediate benzoyl carbodiimide could be isolated by silica gel column flash chromatography in moderate yield.

Key words

sulfones - phosphorus - azides - functionalized guanidines - palladium catalysis

• References


For reviews, see:
• 1a Zhang W.-X. Hou Z. Org. Biomol. Chem. 2008; 6: 1720
• 1b Alonso-Moreno C. Antiñolo A. Carrillo-Hermosilla F. Otero A. Chem. Soc. Rev. 2014; 43: 3406
• 1c Zhang W.-X. Xu L. Xi Z. Chem. Commun. 2015; 51: 254
• 2 For an example, see: Lange JH. Coolen HK. Van Stuivenberg HH. Dijksman JA. Herremans AH. Ronken E. Keizer HG. Tipker K. Mccreary AC. Veerman W. Wals HC. Stork B. Verveer PC. Den Hartog AP. De Jong NM. Adolfs TJ. Hoogendoorn J. Kruse CG. J. Med. Chem. 2004; 47: 627
• 3 For an example, see: Lebedeva NA. Anarbaev RO. Kupryushkin MS. Rechkunova NI. Pyshnyi DV. Stetsenko DA. Lavrik OI. Bioconjugate Chem. 2015; 26: 2046

For examples, see:
• 4a Murtaza G. Rauf MK. Badshah A. Ebihara M. Said M. Gielen M. De Vos D. Dilshad E. Mirza B. Eur. J. Med. Chem. 2012; 48: 26
• 4b Gul R. Badshah A. Khan A. Junaid A. Rauf MK. Spectrochim. Acta, Part A 2014; 117: 264
• 5a Henry RJ. Bacteriol. Rev. 1943; 7: 175
• 5b Hu SX. Mazur CA. Feenstra KL. Lorenz JK. Merritt DA. Vet. J. 2016; 211: 26
• 6 Rudrawar S. Dyason JC. Rameix-Welti M.-A. Rose FJ. Kerry PS. Russell RJ. M. van der Werf S. Thomson RJ. Naffakh N. von Itzstein M. Nat. Commun. 2010; 1: 113
• 7a Zhang J. Shi Y. Tetrahedron Lett. 2000; 41: 8075
• 7b Cunha S. Costa MS. B. Napolitano HB. Lariucci C. Vencato I. Tetrahedron 2001; 57: 1671
• 7c Souza MC. Macedo WP. Silva MC. M. Ramos GC. D. O. Alt HG. Phosphorus, Sulfur Silicon Relat. Elem. 2004; 179: 1047
• 7d Cunha S. Rodrigues MT. Tetrahedron Lett. 2006; 47: 6955
• 7e Tan D. Mottillo C. Katsenis AD. Štrukil V. Friščič T. Angew. Chem. Int. Ed. 2014; 53: 9321
• 7f Esteves H. de Fátima A. Castro R. dP. Sabino JR. Macedo F. Brito TO. Tetrahedron Lett. 2015; 56: 6872

For selected reviews, see:
• 8a Bräse S. Gil C. Knepper K. Zimmermann V. Angew. Chem. Int. Ed. 2005; 44: 5188
• 8b Bräse S. Banert K. Organic Azides: Syntheses and Applications . Wiley-VCH; Weinheim: 2010
• 8c Driver TG. Org. Biomol. Chem. 2010; 8: 3831
• 8d Intrieri D. Zardi P. Caselli A. Gallo E. Chem. Commun. 2014; 50: 11440
• 8e Shin K. Kim H. Chang S. Acc. Chem. Res. 2015; 48: 1040
• 9a Doi H. Barletta J. Suzuki M. Noyori R. Watanabe Y. Långström B. Org. Biomol. Chem. 2004; 2: 3063
• 9b Ren L. Jiao N. Chem. Commun. 2014; 50: 3706
• 9c Zhao J. Li Z. Song S. Wang MA. Fu B. Zhang Z. Angew. Chem. Int. Ed. 2016; 55: 5545
• 9d Zhao J. Li Z. Yan S. Xu S. Wang MA. Fu B. Zhang Z. Org. Lett. 2016; 18: 1736
• 9e Chow SY. Stevens MY. Odell LR. J. Org. Chem. 2016; 18: 2681
• 10a Cowley RE. Golder MR. Eckert NA. Al-Afyouni MH. Holland PL. Organometallics 2013; 32: 5289
• 10b Wiese S. Aguila MJ. B. Kogut E. Warren TH. Organometallics 2013; 32: 2300
• 10c Zhang Z. Li Z. Fu B. Zhang Z. Chem. Commun. 2015; 51: 16312
• 10d Zhang Z. Xiao F. Huang B. Hu J. Fu B. Zhang Z. Org. Lett. 2016; 18: 908
• 10e Chen K. Tang XY. Shi M. Chem. Commun. 2016; 52: 1967
• 10f Zhang Z. Huang B. Qiao G. Zhu L. Xiao F. Chen F. Bin F. Zhang Z. Angew. Chem. Int. Ed. 2017; 56: 4320
• 10g Gu Z. Liu Y. Wang F. Bao X. Wang S. Ji S. ACS Catal. 2017; 7: 3893
• 11a Negishi E. Handbook of Organopalladium Chemistry for Organic Synthesis. John Wiley & Sons; New York: 2002
• 11b Tsuji J. Palladium Reagents and Catalysts: New Perspectives for the 21st Century. John Wiley & Sons; New York: 2004
• 12a Newman MS. Gildenhorn HL. J. Am. Chem. Soc. 1948; 70: 317
• 12b Linke S. Tisue GT. Lwowski W. J. Am. Chem. Soc. 1967; 89: 6308
• 12c L’abbé G. Chem. Rev. 1969; 69: 345
• 13a Wamhoff H. Bamberg C. Herrmann S. Niegerl M. J. Org. Chem. 1994; 59: 3985
• 13b Larksarp C. Alper H. J. Am. Chem. Soc. 1997; 119: 3709
• 13c Saito T. Sugizaki K. Otani T. Suyama T. Org. Lett. 2007; 9: 1239
• 13d Yu RT. Rovis T. J. Am. Chem. Soc. 2008; 130: 3262
• 13e Wang Z. Wang Y. Zhang W.-X. Hou Z. Xi Z. J. Am. Chem. Soc. 2009; 131: 15108
• 13f Zeng F. Alper H. Org. Lett. 2010; 12: 1188
• 13g Qiu G. He Y. Wu J. Chem. Commun. 2012; 48: 3836
• 13h Rauws TR. M. Maes BU. W. Chem. Soc. Rev. 2012; 41: 2463
• 14 Zhang J. Shi Y. Stein P. Atwal K. Li C. Tetrahedron Lett. 2002; 43: 57
• 15 L’abbé G. Verbruggen A. Minami T. Toppet S. J. Org. Chem. 1981; 46: 4478