T. B. Nguyen et al. / Tetrahedron 62 (2006) 647–651
651
5. In our early studies on the stereocontrolled racemic synthesis
of fungal metabolites thaxtomins A and B, we have reported
that Li2CuCl4 is an efficient catalyst for cross-coupling of
lithiated 1,4-dialkyl-2,5-piperazinedione anions with gramine
methosulfate and alkyl halides: (a) Gelin, J.; Mortier, J.;
4.5.2. Trichloro(nonadec-18-enyl)silane (14). See general
procedure. H NMR (400 MHz, CDCl3) d: 5.80 (m, 1H),
5.02–4.91 (m, 2H), 2.07–2.01 (m, 2H), 1.60–1.54
(m, 2H),1.42–1.29 (m, 30H). 13C NMR (100 MHz,
CDCl3) d: 139.3, 114.1, 33.8, 31.8, 29.7, 29.6, 29.6, 29.5,
29.4, 29.2, 29.03, 29.0, 24.3, 22.3.
1
ˆ
Moyroud, J.; Chene, A. J. Org. Chem. 1993, 58, 3473. (b)
ˆ
Moyroud, J.; Gelin, J.; Chene, A.; Mortier, J. Tetrahedron
1996, 52, 8525.
4.5.3. Triethoxy(tridec-12-enyl)silane (15). Prepared
according to the general procedure from 13-bromo-tridec-
1-ene (11). Colorless oil (67%). 1H NMR (200 MHz, CDCl3)
d: 5.80 (m, 1H), 5.05–4.88 (m, 2H), 3.82 (q, JZ6.8 Hz, 6H),
2.10–1.98 (m, 2H), 1.50–1.20 (m, 27H), 0.67–0.58 (m, 2H).
13C NMR (50 MHz, CDCl3) d: 139.2, 114.0, 58.2, 33.8, 33.2,
29.5, 29.2, 29.1, 28.9, 22.8, 18.2, 10.3. IR (neat): 2973, 2923,
6. Nevertheless, Cu-catalyzed alkylation of secondary and
tertiary alkyl Grignards is facilitated by the presence of
N-methyl pyrrolidone (4–9 equiv). See:
´ ´
Cahiez, G.;
Chaboche, C.; Jezequel, M. Tetrahedron 2000, 56, 2733.
7. The soluble copper catalyst ‘CuBr–LiBr–LiSPh–THF’ is
efficient for coupling primary, secondary, tertiary, aryl,
vinyl, and allylic Grignard reagents to primary tosylates and
primary Grignard reagents to secondary tosylates and
mesylates. See: Burns, D. H.; Miller, J. D.; Chan, H.-K.;
Delaney, M. O. J. Am. Chem. Soc. 1997, 119, 2125.
8. (a) Wasserman, S. R.; Tao, Y.-T.; Whitesides, G. M. Langmuir
1989, 5, 1074. (b) Balachander, N.; Sukenik, C. N. Langmuir
1990, 6, 1621. (c) Effenberger, F.; Heid, S. Synthesis 1995, 1126.
9. See also: (a) Netzer, L.; Iscovici, R.; Sagiv, J. Thin Solid films
1983, 99, 235. (b) Johnson, D. K.; Ciavarri, J. P.; Ishmael,
F. T.; Schillinger, K. J.; Van Geel, T. A. P.; Stratton, S. M.
Tetrahedron Lett. 1995, 36, 8565. (c) Peanaski, J.; Schneider,
H.; Granick, S.; Kessel, C. Langmuir 1995, 11, 953. (d)
Friedman, L.; Shani, A. J. Am. Chem. Soc. 1974, 96, 7101.
10. Bis-coupling reactions of a,u-ditosylates with Grignard
reagents have been reported: Schlosser, M.; Bossert, H.
Tetrahedron 1991, 47, 6287.
2853, 1641, 1441, 1389, 1166, 1102, 1076 cmK1
.
4.5.4. Triethoxy(nonadec-18-enyl)silane (16). Prepared
according to the general procedure from 19-bromononadec-
1-ene (12). Colorless oil (60%). 1H NMR (200 MHz,
CDCl3) d: 5.80 (m, 1H), 5.05–4.88 (m, 2H), 3.82 (q, JZ
6.8 Hz, 6H), 2.10–1.98 (m, 2H), 1.50–1.20 (m, 39H),
0.67–0.58 (m, 2H). 13C NMR (100 MHz, CDCl3) d: 139.20,
114.06, 58.27, 33.82, 33.21, 29.70, 29.63, 29.56, 29.52,
29.27, 29.16, 28.95, 22.75, 18.29, 10.38.
Acknowledgements
´
This research was supported by the CNRS, Universite du
Maine, Agence Universitaire de la Francophonie and
Institut Universitaire de France. We also would like to
thank Professor J. Sagiv et Dr. R. Maoz (Weizmann Institute
of Science, Rehovot) for useful discussions.
11. Nard Chemical Ltd (Hyogo) and Matsushita Electric Industrial
Co. Ltd (Osaka) supply NTS on demand. To the best of our
knowledge, the processes used are neither patented nor
published.
12. Octane-1,8-diol is commercial. For the preparation of tetra-
decane-1,14-diol, see: Rodriguez, M.; Llinares, M.; Doulut, S.;
Heitz, A.; Martinez, J. Tetrahedron Lett. 1991, 32, 923.
13. Chatti, S.;Bortolussi,M.;Loupy,A.Tetrahedron2000, 56, 5877.
14. Organomagnesiums couple efficiently with u-chloroalkyl-p-
toluene sulfonates: see Ref. 10. Reactions of Grignard reagents
with alkylsulfonates: (a) Mori, K.; Takikawa, H. Tetrahedron
1990, 46, 3139. (b) Shirai, Y.; Seki, M.; Mori, K. Eur. J. Org.
Chem. 1999, 3139. (c) Nakamura, Y.; Mori, K. Eur. J. Org.
Chem. 2000, 1307.
References and notes
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stoichiometric relationship within the cuprate.
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Volkmann, R. A.; Davis, J. T.; Meltz, C. N. J. Org. Chem.
21. Under similar conditions, commercial 11-bromoundec-1-ene
gave triethoxy(undec-10-enyl)silane in 65% yield.
¨
1983, 48, 1767. (d) Backwall, J.; Sellen, M.; Grant, B. J. Am.
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