Regioselective aminolysis and hydrolysis of chiral 1,4-ferrocenyl diacetate

Journal of Organic Chemistry

Volumn 69, Issue 15, 2004, Pages 4991-4996

  Fukuzawa, Shin Ichi ^a   Wachi, Daisuke ^a   Suzuki, Takashi ^a   Itoh, Satoshi ^a  

^a CHUO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

CONFORMATIONS; HYDROLYSIS; IONIZATION; STEREOCHEMISTRY; SUBSTITUTION REACTIONS;

REGIOSELECTIVE AMINOLYSIS; STEREOGENIC CENTERS;

ORGANOMETALLICS;

1,2 ACETAMIDOALCOHOL; 1,2 BIS(PHENYLMETHYL)FERROCENYL DIACETATE; 1,4 FERROCENYL DIACETATE; ACETIC ACID DERIVATIVE; ACETOACETIC ACID; ACETOACETIC ACID DERIVATIVE; ACETOXY GROUP; ALCOHOL DERIVATIVE; AMMONIA; ESTER; FERROCENE DERIVATIVE; FUNCTIONAL GROUP; IRON; METHANOL; TETRAHYDROFURAN; UNCLASSIFIED DRUG;

AMINOLYSIS; AQUEOUS SOLUTION; ARTICLE; CHEMICAL REACTION KINETICS; CHIRALITY; CONFORMATIONAL TRANSITION; DIASTEREOISOMER; GEOMETRY; HYDROLYSIS; IONIZATION; OPTICAL ROTATION; ROOM TEMPERATURE; STEREOCHEMISTRY; SUBSTITUTION REACTION; THERMODYNAMICS;

EID: 3543016128     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo049386c     Document Type: Article

References (19)

1. For reviews, see: (a) Hayashi T. Asymmetric Catalysis with Chiral Ferrocenylphosphine Ligands. In Ferrocenes; Togni A., Hayashi, T., Eds.; VCH: Weinheim, 1995; pp 105-142.
2. (b) Togni, A. New Chiral Ferrocenyl Ligands for Asymmetric Catalysis. In Metallocenes; Togni, A., Halterman, R. L., Eds.; VCH, Weinheim, 1998; Vol. 2, pp 689-721.
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5. (a) Fukuzawa, S.; Tsuchiya, D.; Sasamoto, K.; Hirano, H.; Ohtaguchi, M. Eur. J. Org. Chem. 2000, 2877.
6. (b) Fukuzawa, S.; Fujimoto, K. Synlett 2001, 1275.
7. We have succeeded in the X-ray crystallographic analysis of 3 and found that the single-crystal lattice contained two ferrocene trimers which are connected with hydrogen bonds. The two-ferrocene trimers sandwich the benzene of the recrystallization solvent. See Supporting Information.
8. Fukuzawa, S.; Fujimoto, K.; Komuro, Y.; Matuzawa, H. Org. Lett. 2002, 4, 707.
9. Fukuda, T.; Takehara, A,; Haniu, N.; Iwao, M. Tetrahedron: Asymmetry 2000, 11, 4083.
10. A 1,2-disubstituted ferrocene such as 2a and 3 does not have a planar chirality because they have the same substituent.
11. Marquarding, D.; Klussacek, H.; Gokel, G.; Hoffmann, P.; Ugi, I. J. Am. Chem. Soc. 1970, 92, 5389.
12. N1. reaction at this carbon. Kündig, E. P.; Ratni, H.; Crousse, B.; Bernardinelli, G. J. Org. Chem. 2001, 66, 1852.
13. Pearson, A. J. Metallo-organic Chemistry; Wiley: Chichester, 1985; pp 320-321. Iron Compounds in Organic Synthesis; Academic Press: London, 1994; pp 149-150.
14. Pearson, A. J. Metallo-organic Chemistry; Wiley: Chichester, 1985; pp 320-321. Iron Compounds in Organic Synthesis; Academic Press: London, 1994; pp 149-150.
15. The reaction rate of an exo ferrocenyl alcohol with dimethylamine is faster that that of an endo one. Dixneuf, P. Tetrahedron Lett. 1971, 12, 1561.
16. 13C NMR spectrum by comparing other 1,2-disubstituted ferrocene derivatives. As the endo alcoholic carbon appears at 70.5 ppm in compounds 1 and 4a, it is reasonable to assign 70.0 and 72.0 ppm signals as the endo and the exo alcoholic carbon of 3, respectively. The endo acetate carbon appears at 72.5-73.2 in compounds 8 and 9. We assigned signals at 72.2 and 72.5 in 10 as the exo alcoholic carbon and the endo acetate carbon, respectively.
17. The X-ray crystallographic result of meso-18 shows that both acetoxy groups are directed toward exo. See Supporting Information.
18. 3CO), 3.90 (s, Cp), 5.77 (s, CHO), 6.11 (d, J = 7.5 Hz, CHN), 6.84 (d, J = 7.5 Hz, NHCO).
19. The choice of solvent strongly affected on the diastereoselectivity of the addition of Grignard reagent to the chiral o-aminoformylferrocene; the major isomer was the (1R,4S)-amino alcohol 1 in THF (82% de),2b while the major isomer was the (1R,4S)-amino alcohol in diethyl ether (71% de) (unpublished results). The chelation and nonchelation of amino and formyl group to Grignard reagent may be involved in stereoselectivity.