CP-225,917 synthetic studies: unusual hydroboration regioselectivity influenced by remote functional groups

Tetrahedron Letters

Volumn 49, Issue 3, 2008, Pages 504-507

  Ashenhurst, James A ^a   Gleason, James L ^a  

^a MCGILL UNIVERSITY   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL DERIVATIVE; ALKENE DERIVATIVE; BORANE DERIVATIVE; DIMETHYL SULFIDE; FUNCTIONAL GROUP; PHOMOIDRIDE A;

ADDITION REACTION; ARTICLE; COMPLEX FORMATION; HYDROBORATION; OXIDATION; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS;

EID: 37249078083     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tetlet.2007.11.118     Document Type: Article

References (30)

1. Dabrah T.T., Kaneko T., Massefski W., and Whipple E.B. J. Am. Chem. Soc. 119 (1997) 1594
2. Spiegel D.A., Njardarson J.T., McDonald I.M., and Wood J.L. Chem. Rev. 103 (2003) 2691
3. Isakovic L., Ashenhurst J.A., and Gleason J.L. Org. Lett. 3 (2001) 4189
4. Cortez G., Tennyson R., and Romo D. J. Am. Chem. Soc. 123 (2001) 7945
5. Grieco P.A., Gilman S., and Nishizawa M. J. Org. Chem. 30 (1975) 3760
6. Paddon-Row M.W., and Warrener R.N. Tetrahedron Lett. 15 (1974) 3797
7. Tegmo-Larsson I.-M., and Houk K.N. Tetrahedron Lett. 19 (1978) 941
8. Higher reaction temperatures led to a complex mixture which was devoid of any diene containing products.
9. Assignment of stereochemistry of 13 and 14 is by analogy to 16, all of which display nearly identical chemical shifts for the methyl group.
10. Brown H.C., and Zweifel G. J. Am. Chem. Soc. 82 (1960) 4708
11. For reviews, see:. Brown H.C., Kramer G.W., Levy A.B., and Midland M.M. Organic Syntheses via Boranes (1975), Wiley-Interscience, New York
12. Brown H.C., and Ramachandran P.V. Pure. Appl. Chem. 66 (1994) 201
13. Crudden C.M., and Edwards D. Eur. J. Org. Chem. (2003) 4695
14. Vogels C.M., and Westcott S.A. Curr. Org. Chem. 9 (2005) 687
15. For the influence of strong electron withdrawing groups, see:. Brown H.C., Vara Prasad J.V.N., and Zee S.-H. J. Org. Chem. 51 (1986) 439
16. Brown H.C., Chen G.-M., Jennings M.P., and Ramachandran P.V. Angew. Chem., Int. Ed. 38 (1999) 2052
17. Ramachandran P.V., and Jennings M.P. Org. Lett. 3 (2001) 3790
18. Ramachandran P.V., and Jennings M.P. Chem. Commun. (2002) 386
19. For examples where heteroatom direction has been proposed, see:. Lyle R.E., Carle K.R., Ellefson C.R., and Spicer C.K. J. Org. Chem. 35 (1970) 802
20. Mirand C., Massiot G., Le Men-Olivier L., and Levy J. Tetrahedron Lett. 23 (1982) 1257
21. Suzuki K., Miyazawa M., Shimazaki M., and Tsuchihashi G. Tetrahedron 44 (1988) 4061
22. Jung M.E., and Karama U. Tetrahedron Lett. 40 (1999) 7907
23. For a general review on heteroatom directed reactions, see:. Hoveyda A.H., Evans D.A., and Fu G.C. Chem. Rev. 93 (1993) 1307
24. 3 to the alkene.
25. For an example where a remote alkene influences hydroboration selectivity in a 1,2-disubstituted alkene, see:. Ng F., Chiu P., and Danishefsky S.J. Tetrahedron Lett. 39 (1998) 767
26. Computations were conducted using gaussian 03, Revision C.02, Frisch, M. J. et al.; Gaussian: Wallingford, CT, 2004.
27. Long L., Lu X., Tian F., and Zhang Q. J. Org. Chem. 68 (2003) 4495
28. Xu Y.-J., Zhang Y.-F., and Li J.-Q. Chem. Phys. Lett. 421 (2006) 36
29. See Supplementary data for details. No significant charge differences were observed in the transition states leading to 3° boranes.
30. Diketones of form 9 do not readily undergo Baeyer-Villiger oxidation due to steric hinderance about the ketone.