Register      Login
Australian Journal of Chemistry Australian Journal of Chemistry Society
An international journal for chemical science
RESEARCH FRONT

Enabling the Development of N-Heterocyclic Carbene (NHC) Catalyzed Reactions: Practical Methods for the Preparation of 1-Acyl-2-Alkylcycloalkenes from Cycloalkanones

Sarah J. Ryan A , Lisa Candish A , Iván Martínez A and David W. Lupton A B
+ Author Affiliations
- Author Affiliations

A School of Chemistry, Monash University, Clayton 3800, Victoria, Australia.

B Corresponding author. Email: david.lupton@monash.edu

Australian Journal of Chemistry 64(8) 1148-1157 https://doi.org/10.1071/CH11183
Submitted: 5 May 2011  Accepted: 10 June 2011   Published: 19 August 2011

Abstract

The synthesis of 1-acyl-2-alkylcycloalkenes from a variety of cycloalkanones has been achieved via either β-keto enol phosphates or β-bromoenones. Both methods exploit simple and readily scalable transformations allowing the preparation of the desired compounds to be achieved in three, or four steps, respectively. The utility of these strategies has been examined, resulting in the preparation of 17 disubstituted cycloalkenes.


References

[1]  (a) D. Enders, T. Balensiefer, Acc. Chem. Res. 2004, 37, 534.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXisVequ7Y%3D&md5=db021f18ae8da812b6b9bc885ee084a2CAS |
      (b) D. Enders, O. Niemeier, A. Henseler, Chem. Rev. 2007, 107, 5606.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) N. Marion, S. Díez-González, S. P. Nolan, Angew. Chem. Int. Ed. 2007, 46, 2988.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) V. Nair, S. Vellalath, B. P. Babu, Chem. Soc. Rev. 2008, 37, 2691.
         | Crossref | GoogleScholarGoogle Scholar |
      (e) J. L. Moore, T. Rovis, Top. Curr. Chem. 2009, 290, 77.
         | Crossref | GoogleScholarGoogle Scholar |
      (f) E. M. Phillips, A. Chan, K. A. Scheidt, Aldrichim Acta 2009, 42, 55.
      (g) P.-C. Chiang, J. W. Bode, TCI Mail 2011, 149, 2.

[2]  (a) S. J. Ryan, L. Candish, D. W. Lupton, J. Am. Chem. Soc. 2009, 131, 14176.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXhtFCjtrvE&md5=9537793ed7dd5e8e1825476044cd26e4CAS |
      (b) L. Candish, D. W. Lupton, Org. Lett. 2010, 12, 4836.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) S. J. Ryan, L. Candish, D. W. Lupton, J. Am. Chem. Soc. 2011, 133, 4694.
         | Crossref | GoogleScholarGoogle Scholar |

[3]  (a) K. Y-K. Chow, J. W. Bode, J. Am. Chem. Soc. 2004, 126, 8126.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2cXkvVSjtLc%3D&md5=4ac98b0704d25566d856282ea151ddcfCAS |
      (b) N. T. Reynolds, J. Read de Alaniz, T. Rovis, J. Am. Chem. Soc. 2004, 126, 9518.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) C. Burstein, F. Glorius, Angew. Chem. Int. Ed. 2004, 43, 6205.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) S. S. Sohn, E. L. Rosen, J. W. Bode, J. Am. Chem. Soc. 2004, 126, 1437 0.
         | Crossref | GoogleScholarGoogle Scholar |
      (e) A. Chan, K. A. Scheidt, Org. Lett. 2005, 7, 905.
         | Crossref | GoogleScholarGoogle Scholar |
      (f) K. Zeitler, Org. Lett. 2006, 8, 637.
         | Crossref | GoogleScholarGoogle Scholar |
      (g) B. E. Maki, A. Chan, E. M. Phillips, K. A. Scheidt, Org. Lett. 2007, 9, 371.
         | Crossref | GoogleScholarGoogle Scholar |
      (h) H. U. Vora, T. Rovis, J. Am. Chem. Soc. 2007, 129, 13796.
         | Crossref | GoogleScholarGoogle Scholar |
      (i) B. E. Maki, E. V. Patterson, C. J. Cramer, K. A. Sheidt, Org. Lett. 2009, 11, 3942.
         | Crossref | GoogleScholarGoogle Scholar |
      (j) E. M. Phillips, M. Wadamoto, H. S. Roth, A. W. Ott, K. A. Scheidt, Org. Lett. 2009, 11, 105.
         | Crossref | GoogleScholarGoogle Scholar |
      (k) H. U. Vora, T. Rovis, J. Am. Chem. Soc. 2010, 132, 2860.
         | Crossref | GoogleScholarGoogle Scholar |
      (l) J. Kaeobamrung, J. Mahatthananchai, P. Zheng, J. W. Bode, J. Am. Chem. Soc. 2010, 132, 8810.
         | Crossref | GoogleScholarGoogle Scholar |
      (m) S. De Sarkar, S. Grimme, A. Studer, J. Am. Chem. Soc. 2010, 132, 1190.
         | Crossref | GoogleScholarGoogle Scholar |
      (n) K. Thai, L. Wang, T. Dudding, F. Bilodeau, M. Gravel, Org. Lett. 2010, 12, 5708.
         | Crossref | GoogleScholarGoogle Scholar |
      (o) J. Mahatthananchai, P. Zheng, J. W. Bode, Angew. Chem. Int. Ed. 2011, 50, 1673.
         | Crossref | GoogleScholarGoogle Scholar |

[4]  (a) C. Chen, C.-T. Chien, C.-H. Su, J. Fluor. Chem. 2002, 115, 75.For methods to convert carboxylic acids to acid fluorides see
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XktVaktbY%3D&md5=1db31f93d3a25618453c5e31d80a5878CAS |
      (b) G. A. Olah, M. Nojima, I. Kerekes, Synthesis 1973, 487.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) A. Devos, J. Remion, A.-M. Frisque-Hesbain, A. Colens, L. Ghosez, J. Chem. Soc. Chem. Commun. 1979, 1180.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) G. S. Lal, G. P. Pez, R. J. Pesaresi, F. M. Prozonic, Chem. Commun. (Camb.) 1999, 215.
         | Crossref | GoogleScholarGoogle Scholar |
      (e) F. Beaulieu, L.-P. Beauregard, G. Courchesne, M. Couturier, F. LaFlamme, A. L’Heureux, Org. Lett. 2009, 11, 5050.
         | Crossref | GoogleScholarGoogle Scholar |
      (f) A. L’Heureux, F. Beauulieu, C. Bennett, D. R. Bill, S. Clayton, F. LaFlamme, M. Mirmehrabi, S. Tadayon, D. Tovell, M. Couturier, J. Org. Chem. 2010, 75, 3401.
         | Crossref | GoogleScholarGoogle Scholar |
      (g) J.-G. Kim, D. O. Jang, Synlett 2010, 3049.

[5]  (a) H. O. House, L. J. Czuba, M. Gall, H. D. Olmstead, J. Org. Chem. 1969, 34, 2324.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaF1MXks1Wntb8%3D&md5=60d7b848637b62e0b842552bfcb471c6CAS |
      (b) I. Fleming, J. Goldhill, I. Paterson, Tetrahedron Lett. 1979, 20, 3205.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) I. Fleming, J. Iqbal, Tetrahedron Lett. 1983, 24, 2913.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) J. Iqbal, M. A. Khan, Synth. Commun. 1989, 19, 515.
         | Crossref | GoogleScholarGoogle Scholar |
      (e) S. E. Denmark, J. R. Heemstra, Synlett 2004, 2411.
         | Crossref | GoogleScholarGoogle Scholar |
      (f) S. E. Denmark, J. R. Heemstra, J. Org. Chem. 2007, 72, 5668.
         | Crossref | GoogleScholarGoogle Scholar |

[6]  (a) J. K. Groves, N. Jones, J. Chem. Soc. Sec. C (Organic) 1968, 2898.
         | 1:CAS:528:DyaF1MXhvFKgtg%3D%3D&md5=b00c1dbba4281cc13ad5604a05b26643CAS |
      (b) N. Dufort, B. Jodoin, J. Lafontaine, Can. J. Chem. 1971, 49, 1785.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) R. Vukicevic, S. Konstantinovic, L. Joksovic, G. Ponticelli, M. L. Mihailovic, Chem. Lett. 1995, 24, 275.
         | Crossref | GoogleScholarGoogle Scholar |

[7]  (a) M. Nojima, F. Shiba, M. Yoshimura, N. Tokura, Chem. Lett. 1972, 1, 1133.For preparation see:
         | Crossref | GoogleScholarGoogle Scholar |
      (b) A. Debal, T. Cuvigny, M. Larchevêque, Tetrahedron Lett. 1977, 18, 3187.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) R. L. Danheiser, D. J. Carini, D. M. Fink, A. Basak, Tetrahedron 1983, 39, 935.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) H. J. Ha, K. P. Park, Bull. Korean Chem. Soc. 1988, 9, 411.
      (e) M. E. Krafft, A. M. Wilson, O. A. Dasse, B. Shao, Y. Y. Cheung, Z. Fu, L. V. R. Bonaga, M. K. Mollman, J. Am. Chem. Soc. 1996, 118, 6080.
         | Crossref | GoogleScholarGoogle Scholar |
      (f) B. M. Trost, M. T. Rudd, J. Am. Chem. Soc. 2003, 125, 11516.
         | Crossref | GoogleScholarGoogle Scholar |
      (g) T. Jin, Y. Yamamoto, Org. Lett. 2007, 9, 5259.
         | Crossref | GoogleScholarGoogle Scholar |
      (h) C. Despotopoulou, R. C. Bauer, A. Krasovskiy, P. Mayer, J. M. Stryker, P. Knochel, Chemistry 2008, 14, 2499.
         | Crossref | GoogleScholarGoogle Scholar |
      (i) T. Jin, F. Yang, C. Liu, Y. Yamamoto, Chem. Commun. (Camb.) 2009, 3533.
         | Crossref | GoogleScholarGoogle Scholar |

[8]  (a) F.-W. Sum, L. Weiler, Can. J. Chem. 1979, 57, 1431.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE1MXlslCrtbw%3D&md5=d1ba1d17efb9f7532363e6b6419b28fcCAS |
      (b) M. Alderdice, F.-W. Sum, L. Weiler, Org. Synth. 1984, 62, 14.

[9]  (a) S. Bolvig, P. E. Hansen, Magn. Reson. Chem. 1996, 34, 467.For relative stabilities of enol tautomers of 2-benzoylcyclohexanone (7a), see
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK28Xjs1yksb0%3D&md5=baa0eee2a674bbcc2313c13780ab310bCAS |
      (b) M. Ramos, I. Alkorta, J. Elguero, Tetrahedron 1997, 53, 1403.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) G. E. Tumambac, C. J. Francis, C. Wolf, Chirality 2005, 17, 171.
         | Crossref | GoogleScholarGoogle Scholar |

[10]  (a) C. Wiles, P. Watts, S. J. Haswell, E. Pombo-Villar, Tetrahedron Lett. 2002, 43, 2945.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD38XisFGktLg%3D&md5=8ddd89ac57cd2fd53849634a8efbf75dCAS |
      (b) E. Fos, L. Borràs, M. Gasull, D. Mauleón, G. Carganico, J. Heterocycl. Chem. 1992, 29, 203.
         | Crossref | GoogleScholarGoogle Scholar |

[11]  (a) M. Tamura, J. K. Kochi, J. Am. Chem. Soc. 1971, 93, 1487.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE3MXht1Cnu7w%3D&md5=5d8b1e69a6bfb0814f004100c237240cCAS |
      (b) S. M. Neumann, J. K. Kochi, J. Org. Chem. 1975, 40, 599.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) R. S. Smith, J. K. Kochi, J. Org. Chem. 1976, 41, 502.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) H. M. Walborsky, R. B. Banks, J. Org. Chem. 1981, 46, 5074.
         | Crossref | GoogleScholarGoogle Scholar |
      (e) G. A. Molander, B. J. Rahn, D. C. Shubert, S. E. Bonde, Tetrahedron Lett. 1983, 24, 5449.
         | Crossref | GoogleScholarGoogle Scholar |
      (f) G. Cahiez, H. Avedissian, Synthesis 1998, 1199.
         | Crossref | GoogleScholarGoogle Scholar |

[12]  (a) A. Fürstner, D. De Souza, L. Parra-Rapado, J. T. Jensen, Angew. Chem. Int. Ed. 2003, 42, 5358.For use in total synthesis, see
         | Crossref | GoogleScholarGoogle Scholar |
      (b) A. Fürstner, L. Turet, Angew. Chem. Int. Ed. 2005, 44, 3462.
         | Crossref | GoogleScholarGoogle Scholar |

[13]  (a) Z. Arnold, A. Holy, Collect. Czech. Chem. Commun. 1961, 26, 3059.
         | 1:CAS:528:DyaF38XnvFSisQ%3D%3D&md5=7ef10c237a1a639c162417d103af9bb9CAS |
      (b) I. R. Robertson, J. T. Sharp, Tetrahedron 1984, 40, 3095.
         | Crossref | GoogleScholarGoogle Scholar |
      (c) R. Jana, S. Paul, A. Biswas, J. K. Ray, Tetrahedron Lett. 2010, 51, 273.
         | Crossref | GoogleScholarGoogle Scholar |
      (d) G. Jones, S. P. Stanforth, Org. React. 2000, 56, 355.and references therein

[14]  D. C. Harrowven, D. D. Pascoe, I. L. Guy, Angew. Chem. Int. Ed. 2007, 46, 425.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXotVGjuw%3D%3D&md5=15b92c59ca139e6ad72a029b5caee02eCAS |

[15]  S. V. Pitre, P. S. Vankar, Y. D. Vankar, Tetrahedron 1996, 52, 12291.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK28Xlslent78%3D&md5=af775053a61a8a1aecd526cfc6bc7142CAS |

[16]  L. A. Carpino, A. A. Abdel-Maksoud, D. Ionescu, E. M. E. Mansour, M. A. Zeawil, J. Org. Chem. 2007, 72, 1729.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2sXhtlynsrw%3D&md5=b903ad64ce89dedec3bad99098be3c05CAS |

[17]  M. Murai, S. Yoshida, K. Miki, K. Ohe, Chem. Commun. (Camb.) 2010, 46, 3366.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXlsFanurg%3D&md5=75534e0eefdf7a21840ba0d4977e98edCAS |

[18]  B. Jousseaume, P. Villeneuve, Tetrahedron 1989, 45, 1145.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL1MXltFGgu74%3D&md5=7f6aa50adb90178bf0236ea29f9e4b5fCAS |

[19]  T. Hudlicky, T. Srnak, Tetrahedron Lett. 1981, 22, 3351.
         | Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL38XjsVKgug%3D%3D&md5=25f02d23dfcb356e7eaad8de38d9f0f6CAS |