A. Carpita, L. Mannocci, R. Rossi
FULL PAPER
rahedron Lett. 1996, 37, 8455–8458; b) Ref.[1b]; c) Ref.[1j]; d)
E. J. Corey, G. W. J. Fleet, M. Kato, Tetrahedron Lett. 1973, 14,
3963–3966.
in good agreement with those reported in the literature, and those
of 5e were in good agreement with those of the same compound
we had synthesized from 11.
[3] a) D. L. J. Clive, Y. Tao, Y. Bo, Y.-Z. Hu, N. Selvakumar, S.
Sun, S. Daigneault, Y.-J. Wu, Chem. Commun. 2000, 1341–
1350; b) C. Mukai, I. Nomura, S. Kitagaki, J. Org. Chem. 2003,
68, 1376–1385.
[4] For typical examples, see: a) J. Garcia, M. López, J. Romeu,
Synlett 1999, 429–431; b) W. B. Austin, N. Bilow, W. J. Kel-
leghan, K. S. Y. Lau, J. Org. Chem. 1981, 46, 2280–2286; c)
E. C. Taylor, P. S. Ray, J. Org. Chem. 1988, 53, 35–38; d)
Ref.[1e]; e) Ref.[1f]
[5] W.-Y. Wong, A. W.-M. Lee, C.-K. Wong, G.-L. Lu, H. Zhang,
T. Mo, K.-T. Lam, New J. Chem. 2002, 26, 354–360.
[6] a) T. Nishinaga, Y. Miyata, N. Nodera, K. Komatsu, Tetrahe-
dron 2004, 60, 3375–3382; b) H. Nakanishi, N. Sumi, Y. Aso,
T. Otsubo, J. Org. Chem. 1998, 63, 8632–8633; c) R. B. Miller,
Synth. Commun. 1972, 2, 267–272.
[7] For examples, see: a) M. E. Perlman, K. A. Watanabe, R. F.
Schinazi, J. J. Fox, J. Med. Chem. 1985, 28, 741–748; b) P. Cas-
ara, C. Danzin, B. Metcalf, M. Jung, J. Chem. Soc., Perkin
Trans. 1 1985, 2201–2207.
1-Ethynyl-4-[(trimethylsilyl)methyl]benzene (5d): The crude reaction
product from the AgNO3-catalysed protiodesilylation of 1d (En-
try 6, Table 2) was purified by MPLC on silica gel with pentane as
eluent to give 5d (1.77 g, 94%) as a colourless liquid. 1H NMR
(200 MHz, CDCl3): δ = –0.02 (s, 9 H), 2.09 (s, 2 H), 3.01 (s, 1 H),
6.94 (d, J = 7.0 Hz, 2 H), 7.35 (d, J = 7.0 Hz, 2 H) ppm. 13C NMR
(50.3 MHz, CDCl3): δ = –1.9 (3C), 27.5, 76.1, 84.1, 117.3, 127.9 (2
C), 131.9 (2 C), 141.9 ppm. IR (film): ν = 3296, 2955, 2107, 1505,
˜
1249, 1152, 851 cm–1. EI-MS: m/z (%) = 188 (37) [M]+, 173 (11),
145 (8), 115 (10), 75 (6), 74 (11), 73 (100). C12H16Si (188.35): calcd.
C 76.53, H 8.56; found C 76.49, H 8.49.
1-[(tert-Butyldimethylsilyl)oxy]-4-ethynylbenzene (5f): The crude re-
action product from the AgNO3-catalysed protiodesilylation of 1f
in acetone and water (Scheme 4) was purified by MPLC on silica
gel with hexane as eluent to give 5f (2.04 g, 88%) as a colourless
1
liquid. H NMR (200 MHz, CDCl3): δ = 0.24 (s, 6 H), 1.02 (s, 9
[8] It should be noted that few examples of protiodesilylation reac-
tions of 1-(trimethylsilyl)-1-alkynes performed in an acidic me-
dium have been reported in the literature: a) M. S. Daly, R. W.
Armstrong, Tetrahedron Lett. 1989, 30, 5713–5716; b) A. B.
Smith, III, S. M. Condon, J. A. McCauley, J. L. Leazer, Jr.,
J. W. Leahy, R. E. Maleczka, Jr., J. Am. Chem. Soc. 1995, 117,
5407–5408; c) O. L. Acevedo, R. S. Andrews, M. Dunkel, P. D.
Cook, J. Heterocycl. Chem. 1994, 31, 989–995; d) L.-X. Gao,
A. Murai, Heterocycles 1996, 42, 745–774.
H), 3.03 (s, 1 H). 6.82 (d, J = 8.8 Hz, 2 H), 7.42 (d, J = 8.8 Hz, 2
H) ppm. 13C NMR (50.3 MHz, CDCl3): δ = –4,4 (2 C), 18.2, 25.7
(3 C), 76.4, 83.7, 114.9, 120.1 (2 C), 133.5 (2 C), 156.2 ppm. IR
(film): ν = 2929, 2109, 1602, 1505, 1264, 912, 841 cm–1. EI-MS:
˜
m/z (%) = 232 (19) [M]+, 177 (6), 176 (24), 175 (100), 159 (3), 145
(5), 115 (4). C14H20OSi (232.40): calcd. C 72.35, H 8.67; found C
72.19, H 8.51.
[9] a) O. Corminboeuf, L. E. Overman, L. D. Pennington, J. Am.
Chem. Soc. 2003, 125, 6650–6652; b) S. Rajagopalan, G. Zwei-
fel, Synthesis 1984, 111–112; c) N. A. Bychkova, N. V. Zotchík,
I. A. Rubtsov, Z. Obshc. Khim. 1983, 54, 1574–1578.
[10] H. M. Schmidt, J. F. Arens, Recl. Trav. Chim. Pays-Bas 1967,
86, 1138–1142.
Acknowledgments
This work was supported by the MIUR (Rome) and the University
of Pisa. We are grateful to Mr. Piergiorgio Vergamini for recording
IR spectra.
[11] For examples concerning the use of this procedure, see: a) G.
Pattenden, M. A. González, P. B. Little, D. S. Millan, A. T.
Plowright, J. A. Tornos, T. Ye, Org. Biomol. Chem. 2003, 1,
4173–4208; b) M. Nazaré, H. Waldmann, Chem. Eur. J. 2001,
7, 3363–3376; c) L. Banfi, G. Guanti, Tetrahedron Lett. 2000,
41, 6523–6526; d) H. Gunji, A. Vasella, Helv. Chim. Acta 2000,
83, 3229–3245; e) J. Alzeer, A. Vasella, Helv. Chim. Acta 1995,
78, 1219–1237; f) M. Alami, S. Guegnot, E. Domingues, G.
Linstrumelle, Tetrahedron 1995, 51, 1209–1220; g) E. T. Jarvi,
J. R. McCarthy, Nucleosides Nucleotides 1994, 13, 585–598; h)
T. Horn, M. Baumgarten, L. Gerghei, V. Enkelmann, K.
Müllen, Tetrahedron Lett. 1993, 34, 5889–5892; i) K. C. Nico-
laou, B. E. Marron, C. A. Veale, S. B. Webber, C. N. Serhan, J.
Org. Chem. 1989, 54, 5527–5535; j) L. D. Foland, O. H. W.
Decker, H. W. Moore, J. Am. Chem. Soc. 1989, 111, 989–995;
k) W. de Graaf, A. Smits, J. Boersma, G. van Koten, W. P. M.
Hoekstra, Tetrahedron 1988, 44, 6699–6704.
Note Added in Proof (March 10, 2005): While this manuscript was
in press, Pale and co-workers published a letter concerning a sub-
ject very similar to that of our study [A. Orsini, A. Vitérisi, A.
Bodlenner, J.-M. Weibel, P. Pale, Tetrahedron Lett. 2005, 46, 2259–
2262].
[1] For examples, see: a) J. E. D. Kirkham, T. D. L. Courtney, V.
Lee, J. E. Baldwin, Tetrahedron Lett. 2004, 45, 5645–5647; b)
F. Bellina, A. Carpita, L. Mannocci, R. Rossi, Eur. J. Org.
Chem. 2004, 2610–2619; c) G. A. Kraus, J. Bae, Tetrahedron
Lett. 2003, 44, 5505–5506; d) A. L. K. Shin Shun, R. R. Tyk-
winski, J. Org. Chem. 2003, 68, 6810–6813; e) Y. Kozawa, M.
Mori, J. Org. Chem. 2003, 68, 8068–8074; f) S.-i. Kusaka, S.
Dohi, T. Doi, T. Takashi, Tetrahedron Lett. 2003, 44, 8857–
8859; g) B. Witulski, C. Alayrac, L. Tevzadze-Saeftel, Angew.
Chem. Int. Ed. 2003, 42, 4257–4260; h) L. Banfi, G. Guanti,
Eur. J. Org. Chem. 2002, 3745–3755; i) S. Gueugnot, M. Alami,
G. Linstrumelle, L. Mambu, Y. Petit, M. Larchevêque, Tetrahe-
dron 1996, 52, 6635–6646; j) R. Rossi, A. Carpita, V. Lippolis,
M. Benetti, Gazz. Chim. Ital. 1990, 120, 783–791; k) M. E.
Jung, J. A. Hagenah, J. Org. Chem. 1987, 52, 1889–1902; l) T.
Sakamoto, Y. Kondo, H. Yamanaka, Heterocycles 1986, 24,
31–32; m) E. J. Corey, J. A. Katzenellenbogen, N. W. Gilman,
S. A. Roman, B. W. Erickson, J. Am. Chem. Soc. 1968, 90,
5618–5620.
[12] M. Shipman, H. R. Thorpe, I. R. Clemens, Tetrahedron 1998,
54, 14265–14282.
[13] A. Köllhofer, H. Plenio, Chem. Eur. J. 2003, 9, 1416–1425.
[14] T. Hundertmark, A. F. Littke, S. L. Buchwald, G. C. Fu, Org.
Lett. 2000, 2, 1729–1731.
[15] X. Lu, C. Cseh, H.-S. Byun, G. Tigyi, R. Bittman, J. Org.
Chem. 2003, 68, 7046–7050.
[16] E. Yashima, S. Huang, T. Matsushima, Y. Okamoto, Macro-
molecules 1995, 28, 4184–4193.
[17] S. Imura, K. Manabe, S. Kobayashi, J. Org. Chem. 2003, 68,
8723–8725.
[2] For examples of removal of the trimethylsilyl group from 1-
(trimethylsilyl)-1-alkynes by treatment with KF·2H2O in DMF,
see: a) V. Fiandanese, G. Marchese, A. Punzi, G. Ruggieri, Tet-
[18] J. R. Doyle, P. E. Slade, M. B. Jonassen, Inorg. Synth. 1960, 6,
216–219.
Received: November 12, 2004
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© 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 2005, 1859–1864