Ab Initio Investigation of the Transition State for Asymmetric Synthesis with Boronic Esters

Journal of Organic Chemistry

Volumn 63, Issue 4, 1998, Pages 914-915

  Mark Midland, M ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 1542548446     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo972041s     Document Type: Article

References (18)

1. Mattesen, D. S. Stereodirected Synthesis with Organoboranes; Springer-Verlag: Berlin, 1995; pp 187-189.
2. Professor E. J. Corey has also proposed that the transition state is incorrect and has suggested that the major product arises from a transition state that is similiar to ours. Corey, E. J.; Barnes-Seeman, D.; Lee, T. W. Tetrahedron Asymmetry 1997, 8, 3711. We thank Professor Corey for a preprint of his manuscript.
3. For reviews, see: (a) Reference 1, Chapter 5. (b) Brown, H. C.; Ramachandran, P. V. Pure Appl. Chem. 1994, 66, 201. (c) Matteson, D. S. Pure Appl. Chem. 1991, 63, 339. (d) Matteson, D. S. Chem. Rev. 1989, 89, 1535. (e) Matteson, D. S. Acc. Chem. Res. 1988, 21, 294.
4. For reviews, see: (a) Reference 1, Chapter 5. (b) Brown, H. C.; Ramachandran, P. V. Pure Appl. Chem. 1994, 66, 201. (c) Matteson, D. S. Pure Appl. Chem. 1991, 63, 339. (d) Matteson, D. S. Chem. Rev. 1989, 89, 1535. (e) Matteson, D. S. Acc. Chem. Res. 1988, 21, 294.
5. For reviews, see: (a) Reference 1, Chapter 5. (b) Brown, H. C.; Ramachandran, P. V. Pure Appl. Chem. 1994, 66, 201. (c) Matteson, D. S. Pure Appl. Chem. 1991, 63, 339. (d) Matteson, D. S. Chem. Rev. 1989, 89, 1535. (e) Matteson, D. S. Acc. Chem. Res. 1988, 21, 294.
6. For reviews, see: (a) Reference 1, Chapter 5. (b) Brown, H. C.; Ramachandran, P. V. Pure Appl. Chem. 1994, 66, 201. (c) Matteson, D. S. Pure Appl. Chem. 1991, 63, 339. (d) Matteson, D. S. Chem. Rev. 1989, 89, 1535. (e) Matteson, D. S. Acc. Chem. Res. 1988, 21, 294.
7. For reviews, see: (a) Reference 1, Chapter 5. (b) Brown, H. C.; Ramachandran, P. V. Pure Appl. Chem. 1994, 66, 201. (c) Matteson, D. S. Pure Appl. Chem. 1991, 63, 339. (d) Matteson, D. S. Chem. Rev. 1989, 89, 1535. (e) Matteson, D. S. Acc. Chem. Res. 1988, 21, 294.
8. Matteson, D. S.; Sadhu, K. M. J. Am. Chem. Soc. 1983, 105, 2077.
9. Tripathy, P. B.; Matteson, D. S. Synthesis 1990, 200.
10. Ditrich, K.; Bube, T.; Stürmer, R.; Hoffmann, R. W. Angew. Chem., Int. Ed. Engl. 1986, 25, 1028.
11. Sadhu, K. M.; Matteson, D. S.; Hurst, G. D.; Kurosky, J. M. Organometallics 1984, 3, 804.
12. For an alternative route to the nonracemic α-halo boronic esters using a chiral Lewis acid, see: Jadhav, P. K.; Man, H.-W. J. Am. Chem. Soc. 1997, 119, 846.
13. Midland, M. M.; Zolopa, A. R.; Halterman, R. L. J. Am. Chem. Soc. 1979, 101, 248.
14. Structures 3 and 4 proved to be difficult to minimize. (Matteson, D. S. Personal communication.)
15. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Robb, M. A.; Cheeseman, J. R.; Keith, T.; Petersson, G. A.; Montgomery, J. A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski, V. G.; Ortiz, J. V.; Foresman, J. B.; Cioslowski, J.; Stefanov, B. B.; Nanayakkara, A.; Challacombe, P.; Peng, C. Y.; Ayala, P. Y.; Chen, W.; Wong, M. W.; Andres, J. L.; Replogle, E. S.; Gomperts, R.; Martin, R. L.; Fox, D. J.; Binkley, J. S.; Defrees, D. J.; Baker, J.; Stewart, J. P.; Head-Gordon, M.; Gonzalez, C.; Pople, J. A. Gaussian 94, Revision E.1, Gaussian, Inc.: Pittsburgh, PA, 1995.
16. Magnesium was used in place of zinc to facilitate the calculations. Magnesium salts have been used for the reaction but they have not been fully investigated. (Matteson, D. S. personal communication.)
17. Transition states were located using the QST3 keyword and were confirmed by the presence of a single negative vibration. This vibration corresponded to the migration of the methyl group from boron to the adjacent carbon and loss of chlorine. The vibrations were visualized using PCVIB from Serena Software. The energies are corrected for the zero point energy.
18. There is some uncertainty in the selectivity with 2,3-butanediol (90% de, ref 7) because of uncertainties with analytical methods and the purity of the starting diol (ref 3e).