Facial Selectivity in the Addition of Lithium Dimethylcuprate to 6-Substituted Tricyclo[5.2.1.02,6]deca-4,8-dienones. Synthesis of β-Substituted Cyclopentenones Using Flash Vacuum Thermolysis

Antonius J. H. Klunder; Andries A. Volkers; Binne Zwanenburg

doi:10.1071/CH14094

RESEARCH ARTICLE

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Facial Selectivity in the Addition of Lithium Dimethylcuprate to 6-Substituted Tricyclo[5.2.1.0^2,6]deca-4,8-dienones. Synthesis of β-Substituted Cyclopentenones Using Flash Vacuum Thermolysis

Antonius J. H. Klunder ^A , Andries A. Volkers ^A and Binne Zwanenburg ^A ^B

+ Author Affiliations

- Author Affiliations

^A Radboud University Nijmegen, Institute for Molecules and Materials, Department of Organic Chemistry, Heyendaalseweg 135, 6525 AJ Nijmegen, The Netherlands.

^B Corresponding author. Email: B.Zwanenburg@science.ru.nl

Australian Journal of Chemistry 67(9) 1243-1250 https://doi.org/10.1071/CH14094
Submitted: 25 February 2014 Accepted: 6 April 2014 Published: 29 April 2014

Abstract

The stereoselectivity of the nucleophilic addition of lithium dimethylcuprate and lithium di-n-pentylcuprate to 6-substituted tricyclo[5.2.1.0^2,6]deca-4,8-dienones was investigated. It was shown that substituents at the 6-position can either exert a steric effect or an electronic effect. Steric approach control predominantly giving the endo product was observed for 6-alkyl substituents. Stereoelectronic control could be adequately rationalised using the Cieplak model. Flash vacuum thermolysis was used to prepare a series of β-substituted cyclopentenoids. The sequence leading to cyclopentenoids has an attractive scope.

References

[1] A. J. H. Klunder, J. Zhu, B. Zwanenburg, Chem. Rev. 1999, 99, 1163.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1MXisVGhtb0%3D&md5=aebb46c5091a26e6be386db58b9f0189CAS |

[2] For a review on retro-Diels-Alder reactions, see: B. Rickborn, Org. React. 1998, 52, 1.
| 1:CAS:528:DyaK1cXktlams7g%3D&md5=387988cfbadf777a2f5d03757986283dCAS |

[3] B. Zwanenburg, A. A. Volkers, A. J. H. Klunder, Aust. J. Chem. 2014, 67, 1234.
| Crossref | GoogleScholarGoogle Scholar |

[5] P. M. M. A. Dols, M. M. H. Verstappen, A. J. H. Klunder, B. Zwanenburg, Tetrahedron 1993, 49, 11353.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2cXjt1arsrg%3D&md5=b414a685c61ca1873385e9e4720258d8CAS |

[6] (a) W. H. Watson, A. Nagl, R. P. Kashyap, V. Vidyasagar, Acta Crystallogr. C 1990, 46, 1265.
         | Crossref | GoogleScholarGoogle Scholar |
      (b) W. B. Smith, A. P. Marchand, S. C. Suri, P. W. Jin, J. Org. Chem. 1986, 51, 3052.
         | Crossref | GoogleScholarGoogle Scholar |

[7] J. Zhu, J. Van der Hoeven, J.-W. Slief, A. J. H. Klunder, B. Zwanenburg, Tetrahedron 1995, 51, 10953.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK2MXosVahsrY%3D&md5=2b9dfe67564e5b27b4bd970c98d12eb4CAS |

[9] A. A. Volkers, A. J. H. Klunder, B. Zwanenburg, Tetrahedron 2009, 65, 389.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXhsVKhsLnF&md5=4846ba57fcfe0a8e7b916a1810ba9dc8CAS |

[10] A. J. H. Klunder, W. B. Huizinga, P. J. M. Sessink, B. Zwanenburg, Tetrahedron Lett. 1987, 28, 357.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL2sXlvFOmtLw%3D&md5=bdf1103f90e7d0359c1b45784268f6d7CAS |

[11] A. J. H. Klunder, A. A. Volkers, B. Zwanenburg, Tetrahedron 2009, 65, 2356.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXit1ais74%3D&md5=a31b2d3986559b3e29c4c914c16ff773CAS |

Facial Selectivity in the Addition of Lithium Dimethylcuprate to 6-Substituted Tricyclo[5.2.1.02,6]deca-4,8-dienones. Synthesis of β-Substituted Cyclopentenones Using Flash Vacuum Thermolysis

Abstract

References

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Facial Selectivity in the Addition of Lithium Dimethylcuprate to 6-Substituted Tricyclo[5.2.1.0^2,6]deca-4,8-dienones. Synthesis of β-Substituted Cyclopentenones Using Flash Vacuum Thermolysis