Chelation-directed asymmetric lithiation and C -Substitution of 1,2,4-butanetriol acetonide

Synlett

Volumn 1995, Issue 9, 1995, Pages 978-980

  Helmke, Hendrik ^a   Hoppe, Dieter ^a  

^a UNIVERSITY OF MÜNSTER   (Germany)

Author keywords

carbamate esters; chiral 1 oxyalkyllithium; diastereoselective lithiation; enantioenriched 1,2,4 alkanetriols

Indexed keywords

EID: 84938402460     PISSN: 09365214     EISSN: 14372096     Source Type: Journal    
DOI: 10.1055/s-1995-5115     Document Type: Article

References (27)

1. D. Hoppe, F. Hintze, P. Tebben, Angew. Chem. 1990, 102, 1457-1459; Angew. Chem. Int. Ed. Engl. 1990, 29, 1422-1424
2. Review: D. Hoppe, F. Hintze, P. Tebben, M. Paetow, H. Ahrens, J. Schwerdtfeger, P. Sommerfeld, J. Haller, W. Guamieri, S. Kolczewski, T. Hense, I. Hoppe, Pure Appl. Chem. 1994, 66, 1479-1486.
3. For an X-ray analysis of a (-)-sparteine-chelate complex see: M. Marsch, K. Harms, O. Zschage, D. Hoppe, G. Boche, Angew. Chem. 1991, 103, 338-339; Angew. Chem. Int. Ed. Engl. 1991, 29, 321-322.
4. For the application to N-Boc-smiao derivatives see: S. T. Kerrick, P. Beak, J. Am. Chem. Soc. 1991, 113, 9708-9710
5. P. Beak, S. T. Kerrick, S. Wu, J. Chu, J. Am. Chem. Soc. 1994, 776, 3231-3139.
6. P. Sommerfeld, D. Hoppe, Synlett 1992, 764-765.
7. M. Paetow, H. Ahrens, D. Hoppe, Tetrahedron Lett. 1992, 33, 5323-5326.
8. W. Guamieri, M. Grehl, D. Hoppe, Angew. Chem. 1994, 106, 1815-1818; Angew. Chem. Int. Ed. Engl. 1994, 33, 1734-1737.
9. R.W. Hoffmann, M. Bewersdorf, Tetrahedron Lett. 1990, 31, 67-70
10. R.W. Hoffmann, M. Bewersdorf, Liebigs Ann. Chem. 1992, 643-653
11. R. Hoffmann, R. Bruckner, Chem, Ber. 1992, 125, 2731-2739
12. M. Lautens, P.H.M. Delanghe, J.B. Goh, C. H. Zhang, J. Org. Chem. 1992, 57, 3270-3272
13. S. Marumoto, I. Kuwajima, J. Am. Chem. Soc. 1993, 775, 9021-9024.
14. 1: 80% yield, colourless oil, [a]D20=-11.4 (c = 5.3, MeOH), 1/8-NMR (CDCI3) 5= 1.35 and 1.37 (s, 3), 1.40 (s, 6), 1.56 and 1.53 (s, 3), 1.92 (m, 2), 3.57 (dd, 1, J = 7.9 Hz), 3.73 (s, 2), 4.08 (dd, 1, 7=6 Hz, 7=7.9 Hz), 4.21 (m, 3).
15. F. Hintze, D. Hoppe, Synthesis 1992, 1216-1218.
16. S. Saito, T. Hasegawa, M. Inaba, R. Nishida, T. Fujii, S. Nomizu, T. Moriwake, Chem. Lett. 1984, 1389-1392.
17. General procedure: An approx. 1.4M solution of sec-butyllithium (1.1 mmol) in hexane/isopentane was added dropwise at-78C to a solution of 1 (1.0 mmol) and TMEDA (procedure A) or (-)-sparteine (procedure
18. (each 1.1 mmol) or no chelating additive (procedure
19. in 5 mL of diethyl ether and stirred for 3h. The electrophile (1.5 mmol) was added and stirring continued for 2 h at-78C. After warming up the reaction mixture to r.t., the usual work-up was performed with 5 mL 2N HC1/5 mL ether, followed by flash chromatography on silica gel with ether/pentane.
20. The stannanes 4a and 5a could not be separated, the ratio was determined by 1/8-NMR spectroscopy. 4a: 3/4-NMR (CDC13) 8 0.12 (s, 3), 1.33 and 1.36 (s, 3), 1.40 (s, 6), 1.53 (s, 3), 2.03 (m, 1), 2.17 (m, 1), 3.52 (dd, 1, 7 = 7.9 Hz), 3.72 (s, 2), 4.06 (dd, 1, 7=5.7 Hz, 7=7.9 Hz), 4.18 (m, 2), 4.60 (m, 1); 5a: 3/8NMR (CDC13) 5 0.11 (s, 3), 1.33 and 1.36 (s, 3), 1.40 (s, 6), 1.53 (s, 3), 2.03 (m, 1), 2.17 (m, 1), 3.52 (dd, 1, 7 = 7.9 Hz), 3.72 (s, 2), 4.06 (dd, 1, 7 =5.7 Hz, 7 =7.9 Hz), 4.18 (m, 2), 4.60 (m, 1).
21. Satisfactory C, H, N analyses (+ 0.3%) were obtained from all new products.
22. S. Masamune, W. Choy, J. S. Petersen, L. R. Sita, Angew. Chem. 1985, 97, 1-31; Angew. Chem. Int. Ed. Engl. 1985, 24, 1-31.
23. T. Ebner, M. Eichelbaum, P. Fischer, C. O. Meese, Arch. Pharm. 1989, 322, 399-403; and references.
24. D. Hoppe, M. Paetow, F. Hintze, Angew. Chem. 1993, 105, 430-432; Angew. Chem. Int. Ed. Engl. 1993, 32, 394-396
25. W. Guamieri, M. Grehl, D. Hoppe, Angew. Chem. 1994, 106, 1815-1818; Angew. Chem. Int. Ed. Engl. 1994, 33, 1734-1737.
26. 8: 45% yield, colourless oil, [a]D20=-18.83 (c = 1.03, MeOH), 1/8-NMR (CDC13) 8 0.10 (s, 9), 1.32 and 1.36 (s, 3), 1.39 (s, 6), 1.53 and 1.52 (s, 3), 1.94-2.16 (m, 2), 3.50, 3.71 (s, 2), 4.05 (dd, 1, 7 =6.0 Hz, 7 =7.6 Hz), 4.15 (m, 1); dr 95 : 5 determined by 1/8-NMR-spectroscopy.
27. The structural assignment is based on the following experiment: The ratio 10 : 11 increased to 92 : 8 when (-)-sparteine was used as additive. This should support the abstraction of the pro-5-proton in precursor 9.