G. Chouraqui, M. Petit, P. Phansavath, C. Aubert, M. Malacria
FULL PAPER
=C(CH3)2], 1.88 [s, 3 H, =C(CH3)], 2.30 (m, 2 H, CH2–CH2), 2.70 136.9 (C), 138.2 (C), 138.3 (C), 213.3 (C=O). HRMS calcd. for
(m, 2 H, CH2–CH2), 2.75 (q, J = 7.1 Hz, 2 H, Me–CH2–), 3.15 [m, C22H26O2 [MNa]: 345.1830; found 345.1855.
2 H, CH2(cyclobutene)], 3.41 [m, 2 H, CH2(cyclobutene)], 5.07 (br.
s, 4 H, CH2–O–CH2), 5.15 (s, 1 H, –CH=) ppm. 13C NMR
(100 MHz, CDCl3, 21 °C): δ = –4.1 (2 CH3), 8.2 (CH3), 17.4 (C),
Acknowledgments
19.5 (3 CH3), 21.8 (CH3), 22.0 (CH3), 26.7 (CH3), 28.0 [CH2–C(O)],
Financial support was provided by CNRS, MRES, and IUF
30.7 (CH2), 32.3 (CH2), 32.4 (CH2), 36.8 (CH2), 72.1 (CH2–O–),
(M. M. is a member of IUF). M. P. thanks Aventis-CNRS for a
72.8 (CH2–O–), 124.0, 124.7 (CH=C), 131.8 (C), 134.3 (C), 135.6
fellowship.
(C), 136.5 (C), 139.6 (C), 140.5 (C), 145.4 (C), 156.7 (C), 202.8
(C=O) ppm. HRMS calcd. for C28H42O2Si [MNa]: 461.2852; found
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461.2850.
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(37): NaHMDS (2 solution in THF, 0.5 mL, 0.95 mmol) was
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added dropwise to a cooled (–40 °C) solution of 36 (320 mg
0.73 mmol) in THF (8 mL). The solution was stirred at this tem-
perature for 1 h and then phenylselenyl chloride (209 mg,
1.09 mmol) was added. The mixture was warmed up to room tem-
perature and stirred until completion of the reaction (TLC). The
reaction mixture was extracted with Et2O, washed with water and
brine, dried with magnesium sulfate, filtered, and concentrated in
vacuo. The crude oil was used without further purification in the
next step. NaHCO3 (92 mg, 1.09 mmol) and NaIO4 (312 mg,
1.46 mmol) were added to a solution of the preceding compound
in MeOH (12 mL)/H2O (1.95 mL)/CH2Cl2 (1.5 mL). The mixture
was stirred until completion of the reaction (TLC). The solution
was diluted with Et2O, washed with water and brine, dried with
magnesium sulfate, filtered, and concentrated in vacuo. The crude
oil was purified by flash chromatography to give compound 37
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(202 mg, 63% over 2 steps) as a yellow oil. IR (ATR): ν = 2925,
˜
2853, 1668, 1607, 1246, 822, 759 cm–1 1H NMR (400 MHz,
.
CDCl3, 21 °C): δ = 0.00 [s, 6 H, Si(CH3)2tBu], 0.79 [s, 9 H,
SiC(CH3)3Me2], 1.51 [s, 3 H, =C(CH3)2], 1.59 [s, 3 H, =C(CH3)2],
1.70 [s, 3 H, =C(CH3)], 2.12 (m, 2 H, CH2–CH2), 2.40 (m, 2 H,
CH2–CH2), 3.00 [m, 2 H, CH2(cyclobutene)], 3.13 [m, 2 H, CH2(cy-
clobutene)], 4.92 (br. s, 4 H, CH2–O–CH2), 4.97 (s, 1 H, Si–CH=),
5.83 (dd, J = 10.6, 1.6 Hz, 1 H, H2C=CH), 6.08 (dd, J = 17.5,
1.6 Hz, 1 H, H2C=CH), 6.62 (dd, J = 17.4, 10.6 Hz, 1 H, H2C=CH)
ppm. 13C NMR (100 MHz, CDCl3, 21 °C): δ = –3.8 (2 CH3), 17.7
(C), 19.8 (CH3), 22.1 (CH3) 22.3 (CH3), 26.9 (3 CH3), 28.7 (CH2),
30.8 (CH2), 31.7 (CH2), 32.8 (CH2), 72.4 (CH2O–), 73.1 (CH2O–),
124.5 (C), 125.1 (CH), 130.9 (CH2), 132.1 (C), 135.2 (C), 136.0 (C),
136.5 (C), 137.5 (CH), 139.5 (C), 140.6 (C), 145.3 (C), 156.8 (C),
194.7 (C=O) ppm. HRMS calcd. for C28H40O2Si [MNa]: 459.2675;
found 461.2695.
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[8] For a preliminary account of this work, see: a) P. Phansavath,
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Compound 38: Et2O·BF3 (48% in Et2O, 0.18 mL, 0.69 mmol) was
added to a cooled (–50 °C) solution of 37 (60 mg, 0.14 mmol) in
CHCl3 (10 mL). The mixture was stirred until completion of the
reaction (TLC). The solution was diluted with Et2O, washed with
NaHCO3 solution and brine, dried with magnesium sulfate, fil-
tered, and concentrated in vacuo. The crude oil was purified by
flash chromatography to give compound 38 (29 mg, 65%) as a
white solid. IR (ATR): ν = 744, 898, 1054, 1456, 1672, 2923 cm–1.
˜
1H NMR (200 MHz, CDCl3, 21 °C): δ = 0.70 [s, 3 H, (CH*3)C=C],
1.18 (s, 3 H, CH*3), 1.24 (s, 3 H, CH*3), 1.58 (m, 2 H, =C–CH2–
CH2), 1.99 (m, 2 H, =C–CH2–CH2), 2.24 (m, 2 H, CH2–CH2), 2.46
(m, 2 H, CH2–CH2–), 2.58 [d, J = 7.1 Hz, 1 H, –CH–C(O)], 3.01
[m, 4 H, CH2(cyclobutene)], 4.90 (s, 2 H, CH2–O), 4.97 (m, 2 H,
CH2–O) ppm. 13C NMR (50 MHz, CDCl3, 21 °C): δ = 19.3 (CH3),
23.8 (CH3), 23.8 (CH2), 26.5 (CH2), 26.8 (CH2), 27.3 (CH2), 27.4
(CH3), 28.7 (C), 28.9 (CH2), 29.5 (CH2), 61.8 (CH), 70.9 (CH2–O),
71.7 (CH2–O), 126.3 (C), 130.8 (C), 131.1 (C), 132.3 (C), 134.5 (C),
[9] CCDC-262002 (11) and -262001 (38) contain the supplemen-
tary crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
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Eur. J. Org. Chem. 2006, 1413–1421