Synthesis of chiral alkynes having 2H or halogen at the secondary or tertiary propargylic stereogenic center by hydrolysis and halogenolysis of optically active allenyltitaniums having axial chirality

Tetrahedron Letters

Volumn 39, Issue 25, 1998, Pages 4555-4558

  An, Duk Keun ^a   Okamoto, Sentaro ^a   Sato, Fumie ^a  

^a TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

Alkynes; Asymmetric synthesis; Halogens and compounds; Titanium and compounds

Indexed keywords

ALCOHOL DERIVATIVE; ALKYNE; HALOGEN; HYDROGEN; TITANIUM DERIVATIVE;

ARTICLE; CHIRALITY; HYDROLYSIS; STEREOCHEMISTRY; SYNTHESIS;

EID: 0032543508     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)00830-2     Document Type: Article

References (29)

1. [1] Okamoto S, An DK, Sato F. Tetrahedron Lett. 1989;39:4551-4554.
2. [2] Furuta K, Ishiguro M, Haruta R, Ikeda N, Yamamoto H. Bull. Chem. Soc. Jpn. 1984;57:2768-2776.
3. [3] Yamamoto Y, Ito W, Maruyama K. J. Chem. Soc., Chem. Commun. 1984;1004-1005.
4. [4] Yamamoto H. In: Trost BM. editor, Comprehensive Organic Synthesis, Oxford: Pergamon Press, 1991;Vol. 2:81-98. This is true not only of allenyltitaniums but also of other organotitaniums having an alkyl, aryl or allyl group, see: Reetz MT. Organotitanium Reagents in Organic Synthesis, Berlin/Heidelberg: Springer-Verlag, 1986.
5. [4] Yamamoto H. In: Trost BM. editor, Comprehensive Organic Synthesis, Oxford: Pergamon Press, 1991;Vol. 2:81-98. This is true not only of allenyltitaniums but also of other organotitaniums having an alkyl, aryl or allyl group, see: Reetz MT. Organotitanium Reagents in Organic Synthesis, Berlin/Heidelberg: Springer-Verlag, 1986.
6. [5] Carlsen PHJ, Katsuki T, Martin VS, Sharpless KB. J. Org. Chem. 1981;46:3936-3938.
7. 2, 130 °C).
8. [7] The value expected by simple extrapolation if the substrate is of 100% e.e.
9. [8] The e.e. value and configuration of 7 were confirmed by the same method applied to 5.
10. 1H-homodecoupling NMR experiment of 11 by irradiation of methylene protons at the β-position showed two diastereomeric peaks at δ 2.88 (a minor isomer) and 2.95 (a major isomer) in a 6 : 94 ratio (88% d.s.). (equation presented)
11. 2H]-1-trimethylsilyl-1,2-heptadiene was co-produced which was easily separated by column chromatography.
12. [11] For other methods for preparation of optically active secondary alkynes, see: Corey EJ, Boaz NW. Tetrahedron Lett. 1984;25:3059-3062. Overman LE, Bell KL, Ito F. J. Am. Chem. Soc. 1984;106:4192-4201. Baker R, Head JC, Swain CJ. J. Chem. Soc., Perkin Trans. 1, 1988;85-97. Clasby MC, Craig D, Marsh A. Angew. Chem., Int. Ed. Engl. 1993;32:1444-1446. Norley M, Kocienski P, Faller A. Synlett, 1996;900-902. Shi Y, Peng LF, Kishi Y. J. Org. Chem. 1997;62:5666-5667. Marshall JA, Wang XJ. J. Org. Chem. 1992;57:1242-1252.
13. [11] For other methods for preparation of optically active secondary alkynes, see: Corey EJ, Boaz NW. Tetrahedron Lett. 1984;25:3059-3062. Overman LE, Bell KL, Ito F. J. Am. Chem. Soc. 1984;106:4192-4201. Baker R, Head JC, Swain CJ. J. Chem. Soc., Perkin Trans. 1, 1988;85-97. Clasby MC, Craig D, Marsh A. Angew. Chem., Int. Ed. Engl. 1993;32:1444-1446. Norley M, Kocienski P, Faller A. Synlett, 1996;900-902. Shi Y, Peng LF, Kishi Y. J. Org. Chem. 1997;62:5666-5667. Marshall JA, Wang XJ. J. Org. Chem. 1992;57:1242-1252.
14. [11] For other methods for preparation of optically active secondary alkynes, see: Corey EJ, Boaz NW. Tetrahedron Lett. 1984;25:3059-3062. Overman LE, Bell KL, Ito F. J. Am. Chem. Soc. 1984;106:4192-4201. Baker R, Head JC, Swain CJ. J. Chem. Soc., Perkin Trans. 1, 1988;85-97. Clasby MC, Craig D, Marsh A. Angew. Chem., Int. Ed. Engl. 1993;32:1444-1446. Norley M, Kocienski P, Faller A. Synlett, 1996;900-902. Shi Y, Peng LF, Kishi Y. J. Org. Chem. 1997;62:5666-5667. Marshall JA, Wang XJ. J. Org. Chem. 1992;57:1242-1252.
15. [11] For other methods for preparation of optically active secondary alkynes, see: Corey EJ, Boaz NW. Tetrahedron Lett. 1984;25:3059-3062. Overman LE, Bell KL, Ito F. J. Am. Chem. Soc. 1984;106:4192-4201. Baker R, Head JC, Swain CJ. J. Chem. Soc., Perkin Trans. 1, 1988;85-97. Clasby MC, Craig D, Marsh A. Angew. Chem., Int. Ed. Engl. 1993;32:1444-1446. Norley M, Kocienski P, Faller A. Synlett, 1996;900-902. Shi Y, Peng LF, Kishi Y. J. Org. Chem. 1997;62:5666-5667. Marshall JA, Wang XJ. J. Org. Chem. 1992;57:1242-1252.
16. [11] For other methods for preparation of optically active secondary alkynes, see: Corey EJ, Boaz NW. Tetrahedron Lett. 1984;25:3059-3062. Overman LE, Bell KL, Ito F. J. Am. Chem. Soc. 1984;106:4192-4201. Baker R, Head JC, Swain CJ. J. Chem. Soc., Perkin Trans. 1, 1988;85-97. Clasby MC, Craig D, Marsh A. Angew. Chem., Int. Ed. Engl. 1993;32:1444-1446. Norley M, Kocienski P, Faller A. Synlett, 1996;900-902. Shi Y, Peng LF, Kishi Y. J. Org. Chem. 1997;62:5666-5667. Marshall JA, Wang XJ. J. Org. Chem. 1992;57:1242-1252.
17. [11] For other methods for preparation of optically active secondary alkynes, see: Corey EJ, Boaz NW. Tetrahedron Lett. 1984;25:3059-3062. Overman LE, Bell KL, Ito F. J. Am. Chem. Soc. 1984;106:4192-4201. Baker R, Head JC, Swain CJ. J. Chem. Soc., Perkin Trans. 1, 1988;85-97. Clasby MC, Craig D, Marsh A. Angew. Chem., Int. Ed. Engl. 1993;32:1444-1446. Norley M, Kocienski P, Faller A. Synlett, 1996;900-902. Shi Y, Peng LF, Kishi Y. J. Org. Chem. 1997;62:5666-5667. Marshall JA, Wang XJ. J. Org. Chem. 1992;57:1242-1252.
18. [11] For other methods for preparation of optically active secondary alkynes, see: Corey EJ, Boaz NW. Tetrahedron Lett. 1984;25:3059-3062. Overman LE, Bell KL, Ito F. J. Am. Chem. Soc. 1984;106:4192-4201. Baker R, Head JC, Swain CJ. J. Chem. Soc., Perkin Trans. 1, 1988;85-97. Clasby MC, Craig D, Marsh A. Angew. Chem., Int. Ed. Engl. 1993;32:1444-1446. Norley M, Kocienski P, Faller A. Synlett, 1996;900-902. Shi Y, Peng LF, Kishi Y. J. Org. Chem. 1997;62:5666-5667. Marshall JA, Wang XJ. J. Org. Chem. 1992;57:1242-1252.
19. 2, using optically active alcohols as a chiral proton source has been reported: Mikami K, Yoshida A. Angew. Chem., Int. Ed. Engl. 1997;36:858-860.
20. [13] Neumann C, Boland W. Helv. Chim. Acta. 1990;73:754-761. Crombie L, Heavers AD. J. Chem. Soc., Perkin Trans, 1, 1992;1929-1937. Church NJ, Young DW. J. Chem. Soc., Chem. Commun. 1994;943-944.
21. [13] Neumann C, Boland W. Helv. Chim. Acta. 1990;73:754-761. Crombie L, Heavers AD. J. Chem. Soc., Perkin Trans, 1, 1992;1929-1937. Church NJ, Young DW. J. Chem. Soc., Chem. Commun. 1994;943-944.
22. [13] Neumann C, Boland W. Helv. Chim. Acta. 1990;73:754-761. Crombie L, Heavers AD. J. Chem. Soc., Perkin Trans, 1, 1992;1929-1937. Church NJ, Young DW. J. Chem. Soc., Chem. Commun. 1994;943-944.
23. 2, 120 °C).
24. 1H NMR and GC analysis of the product obtained after passing through a pad of silica gel.
25. 2, 120 °C) and the enantiomers were detected respectively at the retention times of 5.7 min and 5.6 min. The absolute configuration of 10 depicted in Scheme 5 was assigned on the analogy of the reaction of 3 providing 9.
26. 2 gave a complicated mixture after workup.
27. E2′ halodemetallation reactions of allenylstannyl compounds have been reported. Simo MS, Jean A, Lequan M. J. Organometal. Chem. 1972;35:C23-24. Cochran JC, Kuivila HG. Organometallics, 1982;1:97-103 and references cited therein.
28. E2′ halodemetallation reactions of allenylstannyl compounds have been reported. Simo MS, Jean A, Lequan M. J. Organometal. Chem. 1972;35:C23-24. Cochran JC, Kuivila HG. Organometallics, 1982;1:97-103 and references cited therein.
29. [19] To the best of our knowledge, synthesis of optically active tertiary propargyl halide has not been reported. For preparation of racemic tertiary propargyl halide, see: Bentley TW, Dau-Schmidt JP, Llewellyn G, Mayr H. J. Org. Chem. 1992;57:2387-2392 and references cited therein.