Directed regioselective Ni-catalyzed alkylation and hydride addition of allylic ethers. A remarkable turnover in regioselectivity

Tetrahedron Letters

Volumn 37, Issue 21, 1996, Pages 3613-3616

  Morken, James P ^a   Didiuk, Mary T ^a   Hoveyda, Amir H ^a  

^a BOSTON COLLEGE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE DERIVATIVE;

ALKYLATION; ARTICLE; CATALYSIS; DRUG SYNTHESIS; REACTION ANALYSIS;

EID: 0029994911     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)00660-0     Document Type: Article

References (13)

1. Hoveyda, A. H.; Evans, D. A.; Fu, G. C. Chem. Rev. 1993, 93, 1307-1370.
2. For a recent example, see: Charette, A. B.; Brochu, C. J. Am. Chem. Soc. 1995, 117, 11367-11368.
3. For alkyldiphenylphosphine-directed Rh-catalyzed carbonylation reactions, see: (a) Jackson, R. W.; Perlmutter, P.; Suh, G.-H.; Tasdelen, E. E. Aust. J. Chem. 1991, 44, 951-966 and references cited therein.
4. See also: (b) Stary, I.; Kocovsky, P. J. Am. Chem. Soc. 1989, 111, 4981-4982.
5. Evans, D. A.; Fu, G. C.; Hoveyda, A. H. J. Am. Chem. Soc. 1992, 114, 6671-6679.
6. Didiuk, M. T.; Morken, J. P.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 7273-7274.
7. (a) Kurosawa, H.; Ohnishi, H.; Emoto, M.; Chatani, N.; Kawasaki, Y.; Murai, S.; Ikeda, I. Organometallics 1990, 9, 3038-3042.
8. (b) Kurosawa, H.; Ohnishi, H.; Emoto, M.; Kawasaki, Y.; Murai, S. J. Am. Chem. Soc. 1988, 110, 6272-6273.
9. Tatsumi, K.; Nakamura, A.; Komiya, S.; Yamamoto, A.; Yamamoto, T. J. Am. Chem. Soc. 1984, 106, 8181-8188.
10. Komiya, S.; Abe, Y.; Yamamoto, A.; Yamamoto, T. Organometallics 1983, 2, 1466-1468.
11. 2 proceed smoothly without an internal directing group (for example, 3 with PhMgCl proceeds to afford the alkylation product in 85% yield in 3h, as a 1:1 mixture of regioisomers).
12. Similar arguments may be applied to trigonal bipyramidal complexes, where the alkyl unit (Me in i) and the C3 site occupy apical positions (the two phosphines and C5 would be equatorial). Thus, as indicated by studies of Tatsumi (ref 7), one alkyl group involved in reductive elimination is situated apically and the other equatorially, rendering the C-C bond forming process symmetry-allowed.
13. 3 (10-20 equiv) leads to heterogeneous reaction mixtures (low conversions).