Synthesis 2012; 44(14): 2173-2180
DOI: 10.1055/s-0031-1291048
special topic
© Georg Thieme Verlag Stuttgart · New York

Internal Lewis Acid Assisted Benzoic Acid Catalysis

Tyler J. Auvil
Department of Chemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, USA, Fax: +1(614)2921685   eMail: mattson@chemistry.ohio-state.edu
,
Anita E. Mattson*
Department of Chemistry, The Ohio State University, 100 West 18th Avenue, Columbus, Ohio 43210, USA, Fax: +1(614)2921685   eMail: mattson@chemistry.ohio-state.edu
› Institutsangaben
Weitere Informationen

Publikationsverlauf

Received: 09. März 2012

Accepted: 22. März 2012

Publikationsdatum:
25. Mai 2012 (online)


Abstract

Internal Lewis acid assisted benzoic acid derivatives are introduced as new low-molecular-weight single-hydrogen-bond donor catalysts for the activation of nitroalkenes. Selected 2-borylbenzoic acid derivatives gave good yields of products in the addition of indoles to nitroalkenes. Control experiments suggest that both the internal Lewis acid coordination and the carboxylic acid functionalities are critical to the optimal performance of these catalysts.

Supporting Information

 
  • References

  • 1 Berkessel A, Gröger H. Asymmetric Organocatalysis: From Biomimetic Concepts to Applications in Asymmetric Synthesis. Wiley-VHC; Weinheim: 2005
    • 2a Takemoto Y. Chem. Pharm. Bull. 2010; 58: 593
    • 2b Connon SJ, Kavanagh SA, Piccinini A. Org. Biomol. Chem. 2008; 6: 1339
    • 2c Zhang ZG, Schreiner PR. Chem. Soc. Rev. 2009; 38: 1187
    • 2d Takemoto Y. Org. Biomol. Chem. 2005; 3: 4299
    • 3a Kampen D, Reisinger CM, List B. Top. Curr. Chem. 2010; 291: 385
    • 3b You S, Cai Q, Zeng M. Chem. Soc. Rev. 2009; 38: 2190
    • 3c Akiyama T. Chem. Rev. 2007; 107: 5744
    • 4a So SS, Burkett JA, Mattson AE. Org. Lett. 2011; 13: 716
    • 4b So SS, Auvil TJ, Garza VJ. Org. Lett. 2012; 14: 444

      For examples of internal Lewis acid assisted ureas in the context of molecular recognition, see:
    • 5a Hughes MP, Shang MY, Smith BD. J. Org. Chem. 1996; 61: 4510
    • 5b Hughes MP, Smith BD. J. Org. Chem. 1997; 62: 4492

      For selected recent examples of carboxylic acids operating as hydrogen-bond-donor catalysts, see:
    • 6a Hasimoto T, Kimura H, Nakatsu H, Maruoka K. J. Org. Chem. 2011; 76: 6030
    • 6b Hasimoto T, Kimura H, Maruoka K. Angew. Chem. Int. Ed. 2010; 49: 6844
    • 6c Hashimoto T, Maruoka K. J. Am. Chem. Soc. 2007; 129: 100054
    • 6d Momiyama N, Yamamoto H. J. Am. Chem. Soc. 2005; 127: 1080
  • 7 Comins DL, Brown JD. J. Org. Chem. 1984; 49: 1078
  • 8 Schultz AG, Antoulinakis EG. J. Org. Chem. 1996; 61: 4555
  • 9 Blight BA, Leigh DA, McNab H, Thomson PI. T, Hunter CA. Nat. Chem. 2011; 3: 244
  • 10 Smallheer JM, Corte JR. US 2005228000, 2005

    • For examples of internal activation of carbonyl functionalities with boron in structures similar to 8a, see:
    • 11a Omae I. Appl. Organomet. Chem. 2010; 24: 347
    • 11b Besong G, Jarowicki K, Kocienski PJ, Sliwinski E, Boyle FT. Org. Biomol. Chem. 2006; 4: 2193
    • 11c Liu X.-C, Hubbard JL, Scouten WH. J. Organomet. Chem. 1995; 493: 91
    • 11d Murafuji T, Sugihara Y, Moriya T, Mikata Y, Yano S. New J. Chem. 1999; 23: 683
    • 11e Murafuji T, Sugimoto K, Yanagimoto S, Moriya T, Sugihara Y, Mikata Y, Kato M, Yano S. Heterocycles 2001; 54: 929
    • 11f Toyota S, Asakura M, Sakaue T. Bull. Chem. Soc. Jpn. 2002; 75: 2667
  • 12 The only previously reported addition of methyl indole-4-carboxylate to a nitrostyrene required elevated temperatures, see: Gmeiner P, Sommer J, Höfner G. Arch. Pharm. (Weinheim, Ger.) 1995; 328: 329
  • 13 This proposed mechanism is based on a mechanism for the phosphoric acid catalyzed activation of nitroalkenes for nucleophilic attack by indoles, see: Itoh J, Fuchibe K, Akiyama T. Angew. Chem. Int. Ed. 2008; 47: 4016
  • 14 Pangborn AB, Giardello MA, Grubbs RH, Rosen RK, Timmers FJ. Organometallics 1996; 15: 1518
  • 15 Wrackmeyer B In Modern Magnetic Resonance. Webb GA. Springer; Dordrecht: 2006
  • 16 Berggren K, Davidsson O, Fjellstroem O, Gustafsson D, Hanessian S, Inghardt T, Någård M, Nilsson I, Therrien E, Van Otterlo W. WO 2005058826, 2005
  • 17 Smallheer JM, Corte JR. US 2005228000, 2005
  • 18 LaTorse M.-P, Schmitz C. US 5514719, 1996
  • 19 Kolczewski S, Pinard E. US 2011053904, 2011
  • 20 Ruzié C, Krayer M, Balasubramanian T, Lindsey JS. J. Org. Chem. 2008; 73: 5806
  • 21 Ganesh M, Seidel D. J. Am. Chem. Soc. 2008; 130: 16464
  • 22 Xiang J, Tong H, Yu Y. Synth. Commun. 2011; 41: 372
  • 23 Lu SF, Du DM, Xu J. Org. Lett. 2006; 8: 2115
  • 24 Wu J, Li X, Wu F, Wan B. Org. Lett. 2011; 13: 4834
  • 25 An LT, Zou JP, Zhang LL, Zhang Y. Tetrahedron Lett. 2007; 48: 4297