The Curtin-Hammett principle: Stereoselective radical additions to alkenes

Tetrahedron Letters

Volumn 37, Issue 3, 1996, Pages 351-354

  Roth, Martin ^a   Damm, Wolfgang ^a   Giese, Bernd ^a  

^a UNIVERSITY OF BASEL   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

CYANIDE;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS; STEREOCHEMISTRY; TECHNIQUE; THERMODYNAMICS;

EID: 0030050129     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(95)02153-1     Document Type: Article

References (10)

1. B. Giese, W. Damm, M. Roth, M. Zehnder, Synlett 1992, 441. See also: Y. Yamamoto, S. Nishii, T. Ibuka, J. Am. Chem. Soc. 1988, 110, 617.
2. B. Giese, W. Damm, M. Roth, M. Zehnder, Synlett 1992, 441. See also: Y. Yamamoto, S. Nishii, T. Ibuka, J. Am. Chem. Soc. 1988, 110, 617.
3. J. I. Seemann, Chem. Rev. 1983, 83, 83.
4. The alkenes were synthesized by Knoevenagel condensation of malonodinitrile with suitably substituted aldehydes.
5. The formation of radicals by the sonication method is described in: C. Petrier, C. Dupuy, J. L. Luche, Tetrahedron Lett. 1986, 27, 3149; P. Erdmann, J. Schäfer, R. Springer, H.-G. Zeitz, B. Giese, Helv. Chim. Acta 1992, 75, 638.
6. The formation of radicals by the sonication method is described in: C. Petrier, C. Dupuy, J. L. Luche, Tetrahedron Lett. 1986, 27, 3149; P. Erdmann, J. Schäfer, R. Springer, H.-G. Zeitz, B. Giese, Helv. Chim. Acta 1992, 75, 638.
7. The X-ray structures will be published in Acta Cryst.C.
8. 1) exhibit significant trends in the NMR spectra: Hα (δ: 3.75-4.00), Cα (δ:11.3-14.0), and Cβ (δ:40.9-55.3) appear at lower field in the anti isomer 7 (Cα is the C-atom which is substituted by the two nitrile groups). In addition, the coupling JHβHγ (0.5-1.6 Hz) is slightly smaller in compound 6 than in compound 7.
9. The AM1 calculations of 4A and 4B were carried out using the MOPAC6 program QCPE 455. AM1 calculations: M. J. S. Dewar, E. G. Zoebisch, E. F. Healy, J. J. Stewart, J. Am. Chem. Soc. 1985, 121, 2063.
10. The calculations were carried out with Gaussian 92/DFT, Revision F.2, Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Gill, P. M. W.; Johnson, B. G.; Wong, M. W.; Foresman, J. B.; Robb, M. A.; Head-Gordon, M.; Replogle, E. S.; Gomperts, R.; Andres, J. L.; Raghavachari, K.; Binkley, J. S.; Gonzalez, C.; Martin, R. L.; Fox, D. J.; Defrees, D. J.; Baker, J.; Stewart, J. J. P.; Pople, J. A. Gaussian, Inc., Pittsburgh PA, 1993. The transition state structures 8 and 9 were calculated at the MP2/6-31G*//UHF/3-21G level of theory.