Ruthenium Carbene Mediated [2+2+2] Cyclotrimerizations

Abstract

Second-generation Grubbs’ catalyst and Hoveyda-Grubbs’ catalyst are able to catalyze both crossed [2+2+2] cyclotrimerization of diynes with alkynes and di- or trimerizations of diynes. Selection of the reaction conditions allows us to favor one particular process. The process is selective when applied to unsymmetric diynes.

Key words

cyclization - ruthenium - carbenes - alkynes - arenes

References and Notes

• Reviews:
• 1a Chopade PR. Louie J. Adv. Synth. Catal.  2006,  348:  2307 
• 1b Kotha S. Brahmachary E. Lahiri K. Eur. J. Org. Chem.  2005,  4741 
• 1c Saito S. Yamamoto Y. Chem. Rev.  2000,  100:  2901 
• 1d Agenet N. Busine O. Slowinski F. Gandon V. Aubert C. Malacria M. Org. React.  2007,  68:  1 
• 1e Galan BR. Rovis T. Angew. Chem. Int. Ed.  2009,  48:  2830 
• 1f Yamamoto Y. Curr. Org. Chem.  2005,  9:  503 
• Synthesis of pyridines through [2+2+2] cycloadditions:
• 1g Varela JA. Saa C. Chem. Rev.  2003,  103:  3787 
• 1h Heller B. Hapke M. Chem. Soc. Rev.  2007,  36:  1085 
• Recent examples:
• 2a Bonaga LVR. Zhang HC. Moretto AF. Ye H. Gauthier DA. Li J. Leo GC. Maryanoff BE. J. Am. Chem. Soc.  2005,  127:  3473 
• 2b Gandon V. Leca D. Aechtner T. Vollhardt KPC. Malacria M. Aubert C. Org. Lett.  2004,  6:  3405 
• 2c Petit M. Chouraqui G. Phansavath P. Aubert C. Malacria M. Org. Lett.  2002,  4:  1027 
• 2d Eichberg MJ. Dorta RL. Grotjahn DB. Lamottke K. Schmidt M. Vollhardt KPC. J. Am. Chem. Soc.  2001,  123:  9324 
• 3a Yamamoto Y. Kinpara K. Saigoku T. Nishiyama H. Itoh K. Org. Biomol. Chem.  2004,  2:  1287 
• 3b Yamamoto Y. Arakawa T. Ogawa R. Itoh K. J. Am. Chem. Soc.  2003,  125:  12143 
• 3c Yamamoto Y. Hata K. Arakawa T. Itoh K. Chem. Commun.  2003,  1290 
• 3d Hoven GB. Efskind J. Romming C. Undheim K. J. Org. Chem.  2002,  67:  2459 
• 4a Yamamoto Y. Ogawa R. Itoh K. J. Am. Chem. Soc.  2001,  123:  6189 
• 4b Yamamoto Y. Takagishi H. Itoh K. Org. Lett.  2001,  3:  2117 
• 4c Yamamoto Y. Kinpara K. Saigoku T. Takagishi H. Okuda S. Nishiyama H. Itoh K. J. Am. Chem. Soc.  2005,  127:  605 
• 5 Peters J.-U. Blechert S. Chem. Commun.  1997,  1983 
• 6a Roy R. Das SK. Chem. Commun.  2000,  519 
• 6b Das SK. Roy R. Tetrahedron Lett.  1999,  40:  4015 
• 7 Witulski B. Stengel T. Fernández-Hernández JM. Chem. Commun.  2000,  1965 
• 8 Young DD. Senaiar RS. Deiters A. Chem. Eur. J.  2006,  12:  5563 
• 9 Hoven GB. Efskind J. Romming C. Undheim K.
  J. Org. Chem.  2002,  67:  2459 
• Diynes 1b, 1d, and 1e were prepared by known procedures. Compound 1b:
• 10a Shibata T. Yamashita K. Katayama E. Takagi K. Tetrahedron  2002,  58:  8661 
• Compound 1d:
• 10b Kang S.-K. Baik T.-G. Nulak AN. Ha Y.-H. Lim Y. Park J. J. Am. Chem. Soc.  2000,  122:  11529 
• Compound 1e:
• 10c Sylvester KT. Chirik PK. J. Am. Chem. Soc.  2009,  131:  8772 
• 10d

  For details on the preparation of 1c and 1f, see Supporting Information.

11

Ratio of isomers calculated by integration of well resolved signals in the ^¹H NMR spectrum of the reaction crude

12

The work up of this reaction (entry 5, Table  [³] ) allowed the recovery of 50% of the catalyst used.