L. A. Aronica, S. Terreni, A. M. Caporusso, P. Salvadori
FULL PAPER
Synthesis of Carbonyl Compounds, (Eds.: H. M. Colquhoun, D.
J. Thompson, M. V. Twigg), Plenum New York, 1991.
P. Pino, F. Piacenti, M. Bianchi in Organic Synthesis via
Metal Carbonyls, (Eds.: I. Wender, P. Pino), Wiley: New York,
(CH), 136.54 (Cq), 144.13 (Cq) 147.40 (ϭCH), 160.54 (ϭC), 192.60
(CO). Ϫ GC-MS: m/z (%) ϭ 294 (0.1) [Mϩ], 105 (100). Ϫ IR (neat):
[2] [2a]
˜
ν ϭ 2727, 1687, 1586, 1428, 1251. Ϫ C18H22SiO: calcd. C 76.54, H
7.85; found C 76.68, H 7.61.
[2b]
1977, vol. 2, p. 43. Ϫ
J. K. Stille in Comprehensive Organic
Synthesis; (Ed.: I. Fleming), Pergamon, Oxford, U. K., 1991,
(Z)-2-(Dimethylphenylsilylmethylene)-4-methylhexanal (11f): Yield
vol. 4, p. 913.
1
49% (0.38 g). Ϫ H NMR (200 MHz, CDCl3, 25 °C): δ ϭ 0.51 (s,
[3] [3a]
New Synthesis with Carbon Monoxide, (Ed.: J. P. Falbe),
Springer Verlag, Berlin, 1980. Ϫ [3b] R. L. Pruett, J. Chem. Ed.
1986, 63, 196Ϫ198.
6 H), 0.81 (d, J ϭ 6.3 Hz, 3 H), 0.88 (t, J ϭ 7.3 Hz, 3 H), 1.03Ϫ1.63
(m, 3 H), 2.06 (dd, J ϭ 13.4, J ϭ 8.2 Hz, 1 H), 2.38 (dd, J ϭ 13.4,
J ϭ 5.9 Hz, 1 H), 6.90 (s, 1 H), 7.40Ϫ7.50 (m, 3 H); 7.45Ϫ7.55 (m,
2 H), 9.76 (s, 1 H). Ϫ 13C NMR (50.3 MHz, CDCl3, 25° C): δ ϭ
Ϫ0.07 (CH3), 11.31 (CH3), 18.83 (CH3), 29.38 (CH2), 33.82 (CH),
39.29 (CH2), 128.23 (CH), 129.52 (CH), 133.51 (CH), 138.10 (Cq),
150.32 (ϭCH), 156.21 (ϭC), 193.33 (CO). Ϫ GC-MS: m/z (%) ϭ
245 (57) [Mϩ Ϫ 15], 189 (100). Ϫ IR (neat): ν˜ ϭ 2733, 1686, 1587,
1428, 1258 cmϪ1. Ϫ C16H24SiO: calcd. C 73.79, H 9.29; found C
73.59, H 9.45.
[4] [4a]
B. fell, M. Beutler, Tetrahedron Lett. 1972, 3455Ϫ3456. Ϫ
[4b]
C. Botteghi, C. Salomon, Tetrahedron Lett. 1974,
[4c]
4285Ϫ4288. Ϫ
J. R. Johnson, G. D. Cuny, S. L. Buchwald,
[4d]
Angew. Chem. Int. Ed. Engl. 1995, 34, 1760Ϫ1761. Ϫ
Y.
Ishii, K. Miyashita, K. Kamita, M. Hidai, J. Am. Chem. Soc.
1997, 119, 6448Ϫ6449.
[5] [5a]
T. Mise, P. Hong, H. Yamazaki, Chem. Lett. 1982,
401Ϫ404. Ϫ [5b] P. Hong, T. Mise, H. Yamazaki, J. Organomet.
Chem. 1987, 334, 129Ϫ140. Ϫ
[5c]
P. Deshong, D. R. Sidler, P.
J. Rybczynski, G. A. Slough, A. L. Rheingold, J. Am. Chem.
Soc. 1988, 110, 2575Ϫ2585.
(Z)-2-(Dimethylphenylsilylmethylene)-5-methylheptanal (11g): Yield
64% (0.54 g). Ϫ H NMR (200 MHz, CDCl3, 25 °C): δ ϭ 0.49 (s,
1
[6] [6a]
Y. Tsuji, T. Kondo, Y. Watanabe, J. Mol. Cat. 1987, 40,
6 H), 0.86 (t, J ϭ 7.4 Hz, 3 H), 0.86 (d, J ϭ 5.8 Hz, 3 H), 1.07Ϫ1.48
(m, 5 H), 2.20Ϫ2.40 (m, 2 H), 6.91 (t, J ϭ 1.2 Hz, 1 H), 7.35Ϫ7.45
(m, 3 H), 7.49 (m, 2 H), 9.76 (s, 1 H). Ϫ 13C NMR (50.3 MHz,
CDCl3, 25 °C): δ ϭ Ϫ0.05 (CH3), 11.3 (CH3), 19.1 (CH3), 29.3
(CH2), 29.5 (CH2), 34.4 (CH2), 35.3 (CH), 128.2 (CH), 129.5 (CH),
133.6 (CH), 138.1 (Cq), 148.6 (ϭCH), 157.7 (ϭC), 193.2 (CO). Ϫ
[6b]
295Ϫ303. Ϫ
Lett. 1992, 33, 5369Ϫ5372. Ϫ
Chem. Soc., Perkin Trans. 1 1993, 1031Ϫ1037.
K. Itoh, M. Miura, M. Nomura, Tetrahedron
[6c]
R. Takeuchi, M. Sugiura, J.
[7] [7a]
T. F. Murray, J. R. Norton, J. Am. Chem. Soc. 1979, 101,
[7b]
4107Ϫ4119. Ϫ
Norton, J. Am. Chem. Soc. 1981, 103, 7520Ϫ7528. Ϫ
Mise, P. Hong, H. Yamazaki, J. Org. Chem. 1983, 48, 238Ϫ242.
T. F. Murray, E. G. Samsel, V. Varma, J. R
[7c]
T.
GC-MS: m/z (%) ϭ 259 (3) [Mϩ Ϫ 15], 189 (100). Ϫ IR (neat): ν ϭ
˜
[7d]
2730, 1685, 1590, 1428, 1251 cmϪ1. Ϫ C17H26SiO: calcd. C 74.39,
Ϫ
T. Joh, K. Doyama, T. Shiohara, S. Takahashi, Organo-
metallics 1991, 10, 2493Ϫ2498.
H 9.55; found C 74.17, H 9.38.
[8a] K. Mori, T. Mizoroki, A. Ozaki, Chem. Lett. 1975, 39Ϫ42.
[8]
[8b]
Ϫ
T. Hiyama, N. Wakasa, T. Ueda, T. Kusumoto, Bull.
Synthesis of (R,S)- and (S,Z)-1-(Dimethylphenylsilyl)-2-(1-methyl-
propyl)-1,3-butadiene: SchlosserϪSchaub ‘‘instant ylide’’ (methyl-
triphenylphosphonium bromide, mixture with sodium amide; 2 g,
4.8 mmol) was dissolved in anhydrous THF (15 mL). The solution
was stirred at room temperature for 30 min, and (Z)-2-(Dimethyl-
phenylsilylmethylene)-3-methylpentanal (11c, 0.647 g, 2.5 mmol)
was then added. After 1 h, the reaction mixture was quenched with
a 25% NaOH solution and the aqueous layer was extracted with
diethyl ether. The combined organic materials were dried over
Na2SO4 and concentrated in vacuum. The crude product was trans-
ferred to a centrifuge tube and diluted with hexane. After centrifu-
gation, the organic layer was separated from the solid and the solv-
ent was evaporated under reduced pressure to afford 16 in 95%
(0.58 g) yield. Ϫ [α]2D5 ϭ ϩ16.85 (c ϭ 5.05, hexane). Ϫ 1H NMR
(200 MHz, CDCl3, 25 °C): δ ϭ 0.43 (s, 6 H), 0.91 (t, J ϭ 7.4 Hz,
3 H), 1.12 (d, J ϭ 6.8 Hz, 3 H), 1.31Ϫ1.67 (m, 2 H), 2.58 (sext,
J ϭ 6.8 Hz, 1 H), 5.06 (dt, J ϭ 11.0, J ϭ 1.1 Hz, 1 H), 5.33 (dd,
J ϭ 17.5, J ϭ 1.1 Hz, 1 H), 5.69 (s, 1 H), 6.57 (dd, J ϭ 17.5, J ϭ
11.0 Hz, 1 H), 7.35Ϫ7.45 (m, 3 H), 7.50Ϫ7.60 (m, 2 H). Ϫ 13C
NMR (50.3 MHz, CDCl3, 25 °C): δ ϭ 0.38 (CH3), 11.94 (CH3),
20.36 (CH3), 29.46 (CH2), 37.40 (CH), 113.84 (ϭC), 124.33 (ϭ
CH2), 127.74 (CH), 128.71 (CH), 137.77 (CH), 138.29 (ϭC), 139.97
(Cq), 161.34 (ϭC). Ϫ GC-MS: m/z (%) ϭ 244 (17) [Mϩ], 135 (100).
Chem. Soc. Jpn 1990, 63, 640Ϫ642.
I. Matsuda, A. Ogiso, S. Sato, Y. Izumi, J. Am. Chem. Soc.
1989, 111, 2332Ϫ2333.
[9]
[10]
N. Chatani, S. Murai, Synlett 1996, 414Ϫ424.
[11] [11a] J. Otera, T. Mandai, M. Shiba, T. Saito, K. Shimohata, K.
Takemori, Y. Kawasaky, Organometallics 1983, 2, 332Ϫ336. Ϫ
[11b]
R. Mantione, Y. Leroux, J. Organomet. Chem. 1971, 31,
5Ϫ15.
[12] [12a]
J. Martin, I. Fleming, A. Percival, J. Chem. Soc., Perkin 1
[12b]
1981, 2415Ϫ2434. Ϫ
Chem. Commun. 1976, 679Ϫ680.
J. Martin, I. Fleming, J. Chem. Soc.,
[13]
J. Pillot, J. Dunogues, R. J. Calas, j. Chem. Res, Synop. 1977,
268Ϫ269.
I. Fleming, D. A. Perry, Tetrahedron 1981, 37, 4027Ϫ4034.
M. E. Jung, B. Gaede, Tetrahedron 1979, 35, 621Ϫ625.
T. K. Jones, S. E. Denmark, Helv. Chim. Acta 1983, 66,
2377Ϫ2396.
T. K. Jones, S. E. Denmark, J. Am. Chem. Soc. 1982, 104,
2642Ϫ2645.
I. Fleming, A. Barbero, D. Walter, Chem. Rev. 1997, 97,
2063Ϫ2192 and references therein.
I. matsuda, Y. Fukuta, T. Tsuchihashi, H. Nagashima, K. Itoh,
Organometallics 1997, 16, 4327Ϫ4345.
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
M. P. Doyle, M. S. Shanklin, Organometallics 1994, 13,
1081Ϫ1088.
Ϫ IR (neat): ν ϭ 1556, 1428, 1248, 1112 cmϪ1. Ϫ C16H24SiO: calcd.
˜
I. Ojima, R. J. Donovan, M. Eguchi, W. R. Shay, P. Ingallina,
A. Korda, Q. Zeng, Tetrahedron 1993, 49, 5431Ϫ5444.
C 78.61, H 9.90; found C 78.83, 10.05.
[22] [22a]
J. Zhou, H. Alper, Organometallics 1994, 13, 1586Ϫ1591.
[22b]
Ϫ
N. F. Jain, P. F. Cirillo, J. V. Schaus, J. S. Panek, Tetra-
Acknowledgments
This work was in part financially supported by the Ministero
[22c]
hedron Lett. 1995, 36, 8723Ϫ8726. Ϫ
L. Barfacker, C.
Hollmann, P. Eilbracht, Tetrahedron 1998, 54, 4493Ϫ4506 Ϫ
[22d]
P. Eilbracht, C. Hollmann, A. M. Schmidt, L. Barfacker,
`
dell’Universita e della Ricerca Scientifica e Tecnologica (MURST),
Eur. J. Org. Chem. 2000, 7, 1131Ϫ1135.
Roma, (National Projects n° 9903558918 and n° 9903237832).
[23] [23a] I. Ojima, M. Tzamarioudaki, C. Y. Tsai, J. Am. Chem. Soc.
1994, 116, 3643Ϫ3644. Ϫ [23b] I. Ojima, E. Vidal, M. Tzamari-
oudachi, I. Matsuda, J. Am. Chem. Soc. 1995, 117, 6797Ϫ6798
[24] [24a] I. Ojima, P. Ingallina, R. J. Donovan, N. Clos, Organomet-
[1]
[1a] Palladium Reagents in Organic Synthesis, (Ed.: R. F. Heck),
Academic, New York, 1985, p. 341. Ϫ [1b] Carbonylation: Direct
4328
Eur. J. Org. Chem. 2001, 4321Ϫ4329