Exploiting Guanidine as a Ligand
in Cobalt-Catalyzed Alkyne Cyclotrimerizations

Chad C. Eichman; Jason P. Bragdon; James P. Stambuli

doi:10.1055/s-0030-1259931

LETTER

Exploiting Guanidine as a Ligand in Cobalt-Catalyzed Alkyne Cyclotrimerizations

Chad C. Eichman, Jason P. Bragdon, James P. Stambuli*
Evans Chemical Laboratories, The Ohio State University, 100 West 18th Avenue, Columbus, OH 43210, USA
e-Mail: stambuli@chemistry.ohio-state.edu;

Abstract

All articles of this category

Abstract

The synthesis of polysubstituted arenes is accomplished via the regioselective cyclotrimerization of alkynes utilizing a guanidine-ligated cobalt catalyst.

Key words

alkynes - arenes - cycloaddition - regioselectivity - transition metals

Full Text

References

References and Notes

For reviews, see:

1a Ishikawa T. In Superbases for Organic Synthesis: Guanidines, Amidines, Phosphazines, and Related Organocatalysts Ishikawa T. John Wiley and Sons; Chichester: 2009.

1b Berlinck RGS. Burtoloso ACB. Kossuga MH. Nat. Prod. Rep. 2008, 25: 919

1c Oliver DW. Dormehl IC. Wikberg JES. Dambrova M. Med. Chem. Res. 2004, 13: 427

1d Masic LP. Curr. Med. Chem. 2006, 13: 3627

1e Blondeau P. Segura M. Pérez-Fernández R. de Mendoza J. Chem. Soc. Rev. 2007, 36: 198

1f Berlinck RGS. Nat. Prod. Rep. 1999, 16: 339

2 Mayr LM. Schmid FX. Biochemistry 1993, 32: 7994

3 Young CW. Schochetman G. Hodas S. Balis HE. Cancer Res. 1967, 27: 535

4a Colabufo NA. Berardi F. Contino M. Niso M. Abate C. Perrone R. Tortorella V. Naunyn-Schmiedeberg’s Arch. Pharmacol. 2004, 370: 106

4b Palagiano E. De Marino S. Minale L. Riccio R. Zollo F. Iorizzi M. Carré JB. Debitus C. Lucarain L. Provost J. Tetrahedron 1995, 51: 3675

4c Kourany-Lefoll E. Laprevote O. Sevenet T. Montagnac A. Pais M. Debitus C. Tetrahedron 1994, 50: 3415

5a Seiple IB. Su S. Young IS. Lewis CA. Yamaguchi J. Baran PS. Angew. Chem. Int. Ed. 2010, 49: 1095

5b Aron ZD. Overman LE. J. Am. Chem. Soc. 2005, 127: 3380

5c Overman LE. Rhee YH. J. Am. Chem. Soc. 2005, 127: 15652

6 Breslow R. J. Am. Chem. Soc. 1958, 80: 3719

7a Theberge AB. Whyte G. Frenzel M. Fidalgo LM. Wootton RCR. Huck WTS. Chem. Commun. 2009, 6225

7b Ma X. Zhou Y. Zhang J. Zhu A. Jiang T. Han B. Green Chem. 2008, 10: 59

7c Li S. Lin Y. Cao J. Zhang S. J. Org. Chem. 2007, 72: 4067

7d Li S. Xie H. Zhang S. Lin Y. Xu J. Cao J. Synlett 2005, 1885

7e Luzzio FA. Mayorov AV. Synlett 2003, 532

7f Trost BM. Yasutaka T. J. Am. Chem. Soc. 2001, 123: 7162

For reviews, see:

8a Galan BR. Rovis T. Angew. Chem. Int. Ed. 2009, 48: 2830

8b Gandon V. Aubert C. Malacria M. Chem. Commun. 2006, 2209

8c Chopade PR. Louie J. Adv. Synth. Catal. 2006, 348: 2307

8d Kotha S. Brahmachar E. Lahiri K. Eur. J. Org. Chem. 2005, 4741

8e Malacria M. Aubert C. Renaud JL. Methods of Molecular Transformations, In Science of Synthesis (Houben-Weyl) Vol. 1: Lautens M. Trost BM. Thieme; Stuttgart: 2001. p.439

8f Saito S. Yamamoto Y. Chem. Rev. 2000, 100: 2901

8g Ojima I. Tzamarioudaki M. Li Z. Donovan RJ. Chem. Rev. 1996, 96: 635

8h Lautens M. Klute W. Tam W. Chem. Rev. 1996, 96: 49

8i Grotjahn DB. In Comprehensive Organometallic Chemistry II Vol. 12: Abel EW. Stone FGA. Wilkinson G. Hegedus L. Pergamon Press; Oxford: 1995. p.741

8j Schore NE. In Comprehensive Organic Synthesis Vol. 5: Trost BM. Fleming I. Paquette LA. Pergamon Press; Oxford: 1991. p.1129

8k Vollhardt KPC. Angew. Chem., Int. Ed. Engl. 1984, 23: 539

9a Morohashi N. Yokomakura K. Hattori T. Miyano S. Tetrahedron Lett. 2006, 47: 1157

9b Ozerov OV. Ladipo FT. Patrick BO. J. Am. Chem. Soc. 1999, 121: 7941

10a Gevorgyan V. Radhakrishnan U. Takeda A. Rubina M. Rubin M. Yamamoto Y. J. Org. Chem. 2001, 66: 2835

10b Takeda A. Ohno A. Kadota I. Gevorgyan V. Yamamoto Y. J. Am. Chem. Soc. 1997, 119: 4547

11a Agenet N. Gandon V. Vollhardt KPC. Malacria M. Aubert C. J. Am. Chem. Soc. 2007, 129: 8860

11b Doszczak L. Fey P. Tacke R. Synlett 2007, 753

11c Saino N. Amemiya F. Tanabe E. Kase K. Okamoto S. Org. Lett. 2006, 8: 1439

11d Hilt G. Vogler T. Hess W. Galbiati F. Chem. Commun. 2005, 1474

11e Hilt G. Hess W. Vogler T. Hengst C. J. Organomet. Chem. 2005, 690: 5170

11f Chouraqui G. Petit M. Aubert C. Malacria C. Org. Lett. 2004, 6: 1519

11g Diercks R. Eaton BE. Gürtzgen S. Jalisatgi S. Matzger AJ. Radde RH. Vollhardt KPC. J. Am. Chem. Soc. 1998, 120: 8247

12 Teske JA. Deiters A. Org. Lett. 2008, 10: 2195

13 Takeuchi R. Nakaya Y. Org. Lett. 2003, 5: 3659

14a Yoshida K. Morimoto I. Mitsudo K. Tanaka H. Tetrahedron 2008, 64: 5800

14b Tanaka K. Sagae H. Toyoda K. Noguchi K. Hirano M. J. Am. Chem. Soc. 2007, 129: 1522

14c Tanaka K. Hara H. Nishida G. Hirano M. Org. Lett. 2007, 9: 1907

15a Agenet N. Gandon V. Buisine O. Slowinski F. Aubert C. Malacria M. In Organic Reactions Vol. 68: Rajanbabu TV. Wiley; Hoboken: 2007. p.1

15b Birch SJ. Boss SR. Cole SC. Coles MP. Haigh R. Hitchcock PB. Wheatley AEH. Dalton Trans. 2004, 3568

15c Holman KT. Robinson SD. Sahajpal A. Steed JW. J. Chem. Soc., Dalton Trans. 1999, 15

15d Bailey PJ. Grant KJ. Pace S. Parsons S. Stewart LJ. J. Chem. Soc., Dalton Trans. 1997, 4263

15e Bailey PJ. Mitchell LA. Parsons S. J. Chem. Soc., Dalton Trans. 1996, 2839

16 Boeré RE. Boeré RT. Masuda J. Wolmershäuser G. Can. J. Chem. 2000, 78: 1613

17 Ma B. Snyder JK. Organometallics 2002, 21: 4688

18a Toselli N. Martin D. Achard M. Tenaglia A. Bürgi T. Buono G. Adv. Synth. Catal. 2008, 350: 280

18b Hours AE. Snyder JK. Organometallics 2008, 27: 410

18c Hilt G. Galbiati F. Synthesis 2006, 3589

19

This result further demonstrates the effect of the guanidine ligand on the reaction outcome by providing higher regio-selectivities compared to the ‘ligandless’ system (see results in ref. 11d).

20a Yuan C. Chang C.-T. Axelrod A. Siegel D. J. Am. Chem. Soc. 2010, 132: 5924

20b Kase K. Goswami A. Ohtaki K. Tanabe E. Saino N. Okamoto S. Org. Lett. 2007, 9: 931

20c Varela JA. Saá C. Chem. Rev. 2003, 103: 3787

20d Fatland AW. Eaton BE. Org. Lett. 2000, 2: 3131

Supplementary Material

Supporting Information