New Efficient Synthetic Routes to Enantiomerically Pure Fluoroalkyl (Arylsulfinyl)methyl Imines and Amines

Synlett

Volumn 1996, Issue 9, 1996, Pages 887-889

  Bravo, Pierfrancesco ^a   Cavicchio, Giancarlo ^b   Crucianelli, Marcello ^b   Markovsky, Andrey L ^c   Volonterio, Alessandro ^a   Zanda, Matteo ^a  

^a CNR   (Italy)

^b UNIVERSITY OF L'AQUILA   (Italy)

^c INSTITUTE OF BIOORGANIC CHEMISTRY AND PETROCHEMISTRY   (Ukraine)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0002771955     PISSN: 09365214     EISSN: None     Source Type: Journal    
DOI: 10.1055/s-1996-5593     Document Type: Article

References (24)

1. Fluoroorganic Chemistry: Synthetic challenges and Biomedicinal Rewards; Tetrahedron Symposia-in-Print, Resnati, G.; Soloshonok, V. A. Eds. Tetrahedron 1996, 52, Issue 1. Banks, R. E.; Tatlow, J. C.; Smart, B. E. Organofluorine Chemistry: Principles and Commercial Applications; Plenum Press: New York, 1994. Welch, J. T.; Eswarakrishnan, S. Fluorine in Bioorganic Chemistry; John Wiley & Son Inc: New York, 1991. Filler, R.; Kobayashi, Y.; Yagupolskii, L.M. Biomedical Aspects of Fluorine Chemistry; Elsevier: Amsterdam, 1993.
2. Fluoroorganic Chemistry: Synthetic challenges and Biomedicinal Rewards; Tetrahedron Symposia-in-Print, Resnati, G.; Soloshonok, V. A. Eds. Tetrahedron 1996, 52, Issue 1. Banks, R. E.; Tatlow, J. C.; Smart, B. E. Organofluorine Chemistry: Principles and Commercial Applications; Plenum Press: New York, 1994. Welch, J. T.; Eswarakrishnan, S. Fluorine in Bioorganic Chemistry; John Wiley & Son Inc: New York, 1991. Filler, R.; Kobayashi, Y.; Yagupolskii, L.M. Biomedical Aspects of Fluorine Chemistry; Elsevier: Amsterdam, 1993.
3. Fluoroorganic Chemistry: Synthetic challenges and Biomedicinal Rewards; Tetrahedron Symposia-in-Print, Resnati, G.; Soloshonok, V. A. Eds. Tetrahedron 1996, 52, Issue 1. Banks, R. E.; Tatlow, J. C.; Smart, B. E. Organofluorine Chemistry: Principles and Commercial Applications; Plenum Press: New York, 1994. Welch, J. T.; Eswarakrishnan, S. Fluorine in Bioorganic Chemistry; John Wiley & Son Inc: New York, 1991. Filler, R.; Kobayashi, Y.; Yagupolskii, L.M. Biomedical Aspects of Fluorine Chemistry; Elsevier: Amsterdam, 1993.
4. Fluoroorganic Chemistry: Synthetic challenges and Biomedicinal Rewards; Tetrahedron Symposia-in-Print, Resnati, G.; Soloshonok, V. A. Eds. Tetrahedron 1996, 52, Issue 1. Banks, R. E.; Tatlow, J. C.; Smart, B. E. Organofluorine Chemistry: Principles and Commercial Applications; Plenum Press: New York, 1994. Welch, J. T.; Eswarakrishnan, S. Fluorine in Bioorganic Chemistry; John Wiley & Son Inc: New York, 1991. Filler, R.; Kobayashi, Y.; Yagupolskii, L.M. Biomedical Aspects of Fluorine Chemistry; Elsevier: Amsterdam, 1993.
5. a) Bravo, P.; Crucianelli, M.; Zanda, M. Tetrahedron Lett. 1995, 36, 3043.
6. b) Arnone, A.; Bravo, P.; Capelli, S.; Fronza, G.; Meille, S. V.; Zanda, M.; Cavicchio, G.; Crucianelli, M. J. Org. Chem. 1996, 61, 3375.
7. Bravo, P.; Crucianelli, M.; Fronza, G.; Zanda, M. Synlett 1996, 249.
8. Unpublished results from these laboratories. For a recent report on the preparation of α-fluoro- and -perfluoroalkyl imines from the corresponding fluorinated ketones and aldehydes and benzylamine see: Soloshonok, V. A.; Kirilenko, A. G.; Kukhar, V. P.; Resnati, G. Tetrahedron Lett. 1994, 35, 3119.
9. Tamura, K.; Mizukami, H.; Maeda, K.; Watanabe, H.; Uneyama, K. J. Org. Chem. 1993, 58, 32.
10. Uneyama, K.; Morimoto, O.; Yamashita, F. Tetrahedron Lett. 1989, 30, 4821. However, 2 equiv. of α-lithium methyl p-tolylsulfoxide 3 were necessary for the complete consumption of the starting acetimidoyl chlorides 2, probably because 1 equiv of (R)-3 reacts as a base with the product (R)-1, removing an acidic proton a to the sulfinyl group. Unreacted excess of methyl-p-tolylsulfoxide was almost quantitatively recovered in ep form by flash chromatography (FC) of the crude reaction mixture.
11. 3): δ - 72.1 (s).
12. Kirsanov, A. V. Isv. Akad. Nauk SSSR 1950, 426; Chem. Abstr. 1951, 45, 1503. Horner, L.; Oediger, H. Liebigs Ann. Chem. 1959, 627, 142. Appel, R. Angew. Chem. Internat. Ed. 1975, 14, 801.
13. Kirsanov, A. V. Isv. Akad. Nauk SSSR 1950, 426; Chem. Abstr. 1951, 45, 1503. Horner, L.; Oediger, H. Liebigs Ann. Chem. 1959, 627, 142. Appel, R. Angew. Chem. Internat. Ed. 1975, 14, 801.
14. Kirsanov, A. V. Isv. Akad. Nauk SSSR 1950, 426; Chem. Abstr. 1951, 45, 1503. Horner, L.; Oediger, H. Liebigs Ann. Chem. 1959, 627, 142. Appel, R. Angew. Chem. Internat. Ed. 1975, 14, 801.
15. Kirsanov, A. V. Isv. Akad. Nauk SSSR 1950, 426; Chem. Abstr. 1951, 45, 1503. Horner, L.; Oediger, H. Liebigs Ann. Chem. 1959, 627, 142. Appel, R. Angew. Chem. Internat. Ed. 1975, 14, 801.
16. For a review on the Staudinger reaction see: Gololobov, Y. G.; Kasukhin, L. F. Tetrahedron 1992, 48, 1359.
17. Bravo, P.; Piovosi, E.; Resnati, G. Synthesis 1986, 579.
18. 3P=NCbZ. See ref. 2.
19. Only the monofluoro derivative (R)-1k was obtained by FC as a mixture of imine and enamine tautomers. However, the trifluoro N-hexyl derivative 1e and the difluoro N-phenyl derivative 1i tautomerized to the enamine forms after a few days both neat or in chloroform solution (tautomerization of the latter was complete), as observed by NMR analysis.
20. Studies on the geometry of the C=N bond of the title compounds 1, and on the their imine-enamine tautomerization are presently in progress.
21. 2 were not effective in the reduction of (R)-1c.
22. S)-7 diastereoisomers are respectively produced as major diastereoisomers. See ref. 2.
23. Sakai, T.; Yan, F.; Kashino, S.; Uneyama, K. Tetrahedron 1996, 52, 233.
24. The great likeness between the NMR spectra of 6a and 6c allowed to assign the stereochemistry depicted in Scheme 2 to the diastereoisomers of the former.