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Substituent Effects, Reactant Preorganization, and Ligand Exchange Control the Reactivity in RhI-Catalyzed (5+2) Cycloadditions between Vinylcyclopropanes and Alkynes†

  1. Peng Liu1,
  2. Paul Ha-Yeon Cheong Dr.1,
  3. Zhi-Xiang Yu Prof. Dr.2,
  4. Paul A. Wender Prof. Dr.3,
  5. Kendall N. Houk Prof. Dr.1

Article first published online: 15 APR 2008

DOI: 10.1002/anie.200800420

Issue

Angewandte Chemie International Edition

Angewandte Chemie International Edition

Volume 47, Issue 21, pages 3939–3941, May 13, 2008

Additional Information

How to Cite

Liu, P., Cheong, P.-Y., Yu, Z.-X., Wender, Paul A. and Houk, Kendall N. (2008), Substituent Effects, Reactant Preorganization, and Ligand Exchange Control the Reactivity in RhI-Catalyzed (5+2) Cycloadditions between Vinylcyclopropanes and Alkynes. Angew. Chem. Int. Ed., 47: 3939–3941. doi: 10.1002/anie.200800420

Author Information

  1. 1

    Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA 90095-1569, USA, Fax: (+1) 310-206-1843 http://www.chem.ucla.edu/dept/Faculty/houk/

  2. 2

    Beijing National Laboratory for Molecular Sciences (BNLMS), Key Laboratory of Bioorganic Chemistry and Molecular Engineering of the Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China

  3. 3

    Department of Chemistry, Stanford University, Stanford, CA 94305-5080, USA

  1. †

    We are grateful to the National Science Foundation for financial support of this research (CHE-0548209, CHE-0450638, and CHE-0131944). Calculations were performed on the National Science Foundation Terascale Computing System at the NCSA and on the UCLA ATS Cluster. P.H.-Y.C. is grateful for discussions with the new-reactions subgroup of the Wender labs.

Publication History

  1. Issue published online: 6 MAY 2008
  2. Article first published online: 15 APR 2008
  3. Manuscript Received: 27 JAN 2008

Funded by

  • National Science Foundation. Grant Numbers: CHE-0548209, CHE-0450638, CHE-0131944

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Keywords:

  • cycloaddition;
  • density functional calculations;
  • reactivity;
  • rhodium
Thumbnail image of graphical abstract

Heteroatom and bulky alkyl substituents dramatically increase the rate of RhI-catalyzed (5+2) cycloadditions of 1. This fact could be attributed to steric effects which ease the reactant preorganization, and to the stabilization of the allyl intermediate by (hyper)conjugation with the substituents. The methoxy- and isopropyl-substituted 1 have an activation energy 5 and 7 kcal mol−1, respectively, lower than the unsubstituted vinylcyclopropane.

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