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organic compounds
4-Butyl-3-(3,5-dimethoxyphenyl)-4-methoxy-2-(triisopropylsilyl)cyclopent-2-enone
aSchool of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, People's Republic of China, and bChangzheng Hospital, Tianjin 300120, People's Republic of China
*Correspondence e-mail: tju3106@163.com
The title molecule, C27H44O4Si, bears a bulky triisopropylsilyl group. The cyclopentene ring adopts an the plane of its four coplanar C atoms and the benzene ring make a dihedral angle of 73.2 (6)°.
Related literature
For related literature, see: Allen et al. (1987); Frontier & Collison (2005
); Geis & Schmalz (1998
); Roberts et al. (2002
); Shi et al. (2005
); Tanaka & Fu (2001
); Li et al. (2007
, 2008
).
Experimental
Crystal data
|
Data collection: CrystalClear (Rigaku, 2005); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008
); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008
); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: CrystalStructure (Rigaku, 2005).
Supporting information
10.1107/S1600536808002055/rk2071sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808002055/rk2071Isup2.hkl
A solution of the tricarbonyl chromium complexed silyl vinylketene (0.5 mmol) and CH2I2 or Br2CHCH3 (0.75 mmol) in 5 ml of Et2O was cooled to 195 K. The n–BuLi (0.75 mmol) was added within 10 min by syringe. After stirring at 195 K for 1 h, the solution was allowed to warm to room temperature and stirred overnight. The resulting solution was diluted with 30 ml of Et2O and extracted with saturated NaCl (3 × 10 ml). The aqueous layer was backextracted with Et2O (3 × 10 ml). The combined organic layer was dried over anhydrous Na2SO4. After filtration, the solvent was removed under reduced pressure and the residue was purified via flash
(SiO2) to afford the cyclopentenone compound (yield 78%, m.p. 332–333 K). 1H NMR (CDCl3): 6.46 (t, 1H), 6.36 (d, 2H), 3.79 (s, 6H), 3.24 (s, 3H), 2.66 (d, 1H), 2.42 (d, 1H), 1.68–1.63 (m, 1H), 1.44–1.39 (m, 1H), 1.35–1.12 (m, 7H), 0.98 (d, 9H), 0.94 (d, 9H), 0.84 (t, 3H) p.p.m.; 13C NMR (CDCl3): 210.0, 183.3, 159.8, 143.0, 137.5, 106.2, 100.2, 87.0, 55.3, 50.7, 42.2, 36.9, 26.5, 23.0, 19.2, 19.1, 14.0, 11.4 p.p.m..All H atoms were placed in calculated positions and refined as riding, with C—H = 0.95–1.00Å and with Uiso(H) = 1.2 Ueq(C).
Data collection: CrystalClear (Rigaku, 2005); cell
CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: CrystalStructure (Rigaku, 2005).C27H44O4Si | F(000) = 2016 |
Mr = 460.71 | Dx = 1.148 Mg m−3 |
Monoclinic, C2/c | Melting point = 332–333 K |
Hall symbol: -C 2yc | Mo Kα radiation, λ = 0.71070 Å |
a = 39.294 (4) Å | Cell parameters from 374 reflections |
b = 8.3327 (10) Å | θ = 1.9–27.9° |
c = 29.274 (3) Å | µ = 0.12 mm−1 |
β = 146.207 (8)° | T = 113 K |
V = 5331.1 (15) Å3 | Block, colourless |
Z = 8 | 0.26 × 0.24 × 0.10 mm |
Rigaku Saturn diffractometer | 6356 independent reflections |
Radiation source: rotating anode | 5271 reflections with I > 2σ(I) |
Confocal monochromator | Rint = 0.051 |
Detector resolution: 7.31 pixels mm-1 | θmax = 27.9°, θmin = 1.9° |
ω scans | h = −51→49 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −10→10 |
Tmin = 0.961, Tmax = 0.988 | l = −37→38 |
32688 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.049 | H-atom parameters constrained |
wR(F2) = 0.123 | w = 1/[σ2(Fo2) + (0.0613P)2 + 2.2212P] where P = (Fo2 + 2Fc2)/3 |
S = 1.09 | (Δ/σ)max = 0.001 |
6356 reflections | Δρmax = 0.29 e Å−3 |
291 parameters | Δρmin = −0.34 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 1997), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0029 (3) |
C27H44O4Si | V = 5331.1 (15) Å3 |
Mr = 460.71 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 39.294 (4) Å | µ = 0.12 mm−1 |
b = 8.3327 (10) Å | T = 113 K |
c = 29.274 (3) Å | 0.26 × 0.24 × 0.10 mm |
β = 146.207 (8)° |
Rigaku Saturn diffractometer | 6356 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 5271 reflections with I > 2σ(I) |
Tmin = 0.961, Tmax = 0.988 | Rint = 0.051 |
32688 measured reflections |
R[F2 > 2σ(F2)] = 0.049 | 0 restraints |
wR(F2) = 0.123 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.29 e Å−3 |
6356 reflections | Δρmin = −0.34 e Å−3 |
291 parameters |
Geometry. All s.u.'s (except the s.u.'s in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R–factor wR and goodness of fit S are based on F2, conventional R–factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R–factors(gt) etc. and is not relevant to the choice of reflections for refinement. R–factors based on F2 are statistically about twice as large as those based on F, and R–factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
Si1 | 0.060076 (17) | 0.46916 (5) | 0.45150 (2) | 0.01708 (12) | |
O1 | 0.14533 (5) | 0.38982 (14) | 0.63443 (6) | 0.0260 (3) | |
O2 | 0.22955 (5) | 0.04752 (12) | 0.61756 (6) | 0.0191 (2) | |
O3 | 0.13563 (5) | 0.06140 (13) | 0.35883 (7) | 0.0249 (3) | |
O4 | 0.21072 (5) | 0.59302 (13) | 0.45866 (7) | 0.0257 (3) | |
C1 | 0.16047 (6) | 0.32410 (18) | 0.61599 (8) | 0.0185 (3) | |
C2 | 0.13558 (6) | 0.35913 (17) | 0.54188 (8) | 0.0162 (3) | |
C3 | 0.17437 (6) | 0.29104 (16) | 0.55487 (8) | 0.0148 (3) | |
C4 | 0.22794 (6) | 0.20168 (17) | 0.63719 (8) | 0.0166 (3) | |
C5 | 0.20858 (6) | 0.19464 (18) | 0.66571 (8) | 0.0198 (3) | |
H5A | 0.1914 | 0.0881 | 0.6542 | 0.024* | |
H5B | 0.2437 | 0.2170 | 0.7253 | 0.024* | |
C6 | 0.17257 (6) | 0.30081 (16) | 0.50223 (8) | 0.0153 (3) | |
C7 | 0.15364 (6) | 0.16823 (17) | 0.45500 (8) | 0.0171 (3) | |
H7 | 0.1411 | 0.0716 | 0.4555 | 0.021* | |
C8 | 0.15356 (6) | 0.18095 (17) | 0.40790 (8) | 0.0184 (3) | |
C9 | 0.17267 (6) | 0.32121 (18) | 0.40742 (8) | 0.0192 (3) | |
H9 | 0.1727 | 0.3280 | 0.3751 | 0.023* | |
C10 | 0.19146 (6) | 0.44980 (17) | 0.45446 (9) | 0.0179 (3) | |
C11 | 0.19134 (6) | 0.44033 (17) | 0.50188 (8) | 0.0179 (3) | |
H11 | 0.2042 | 0.5297 | 0.5339 | 0.021* | |
C12 | 0.11224 (8) | −0.08178 (19) | 0.35246 (11) | 0.0313 (4) | |
H12A | 0.1013 | −0.1574 | 0.3159 | 0.038* | |
H12B | 0.0758 | −0.0566 | 0.3300 | 0.038* | |
H12C | 0.1435 | −0.1301 | 0.4070 | 0.038* | |
C13 | 0.21186 (7) | 0.6089 (2) | 0.41147 (10) | 0.0250 (3) | |
H13A | 0.2264 | 0.7164 | 0.4195 | 0.030* | |
H13B | 0.1705 | 0.5931 | 0.3532 | 0.030* | |
H13C | 0.2394 | 0.5282 | 0.4292 | 0.030* | |
C14 | 0.27015 (7) | −0.06577 (18) | 0.68287 (9) | 0.0252 (3) | |
H14A | 0.2682 | −0.1668 | 0.6636 | 0.030* | |
H14B | 0.2582 | −0.0848 | 0.7014 | 0.030* | |
H14C | 0.3120 | −0.0237 | 0.7286 | 0.030* | |
C15 | 0.28884 (6) | 0.29106 (17) | 0.69819 (8) | 0.0180 (3) | |
H15A | 0.3219 | 0.2273 | 0.7494 | 0.022* | |
H15B | 0.2975 | 0.2968 | 0.6746 | 0.022* | |
C16 | 0.29095 (7) | 0.46110 (18) | 0.72010 (9) | 0.0214 (3) | |
H16A | 0.2767 | 0.4582 | 0.7364 | 0.026* | |
H16B | 0.2623 | 0.5297 | 0.6707 | 0.026* | |
C17 | 0.35466 (7) | 0.53686 (19) | 0.78964 (9) | 0.0233 (3) | |
H17A | 0.3534 | 0.6409 | 0.8046 | 0.028* | |
H17B | 0.3837 | 0.4662 | 0.8384 | 0.028* | |
C18 | 0.37830 (8) | 0.5645 (2) | 0.76797 (11) | 0.0303 (4) | |
H18A | 0.4193 | 0.6120 | 0.8151 | 0.036* | |
H18B | 0.3506 | 0.6374 | 0.7209 | 0.036* | |
H18C | 0.3803 | 0.4618 | 0.7539 | 0.036* | |
C19 | 0.07163 (7) | 0.69311 (19) | 0.47085 (10) | 0.0267 (3) | |
H19 | 0.0304 | 0.7438 | 0.4214 | 0.032* | |
C20 | 0.11217 (9) | 0.7634 (2) | 0.47859 (13) | 0.0409 (5) | |
H20A | 0.0967 | 0.7301 | 0.4313 | 0.049* | |
H20B | 0.1542 | 0.7244 | 0.5293 | 0.049* | |
H20C | 0.1117 | 0.8808 | 0.4801 | 0.049* | |
C21 | 0.09602 (12) | 0.7453 (2) | 0.54452 (14) | 0.0511 (6) | |
H21A | 0.0701 | 0.7004 | 0.5398 | 0.061* | |
H21B | 0.0956 | 0.8627 | 0.5460 | 0.061* | |
H21C | 0.1380 | 0.7064 | 0.5951 | 0.061* | |
C22 | 0.01096 (6) | 0.39689 (19) | 0.44564 (9) | 0.0225 (3) | |
H22 | 0.0294 | 0.4441 | 0.4944 | 0.027* | |
C23 | 0.01070 (8) | 0.2140 (2) | 0.45283 (11) | 0.0313 (4) | |
H23A | 0.0529 | 0.1748 | 0.5017 | 0.038* | |
H23B | −0.0103 | 0.1617 | 0.4038 | 0.038* | |
H23C | −0.0107 | 0.1890 | 0.4576 | 0.038* | |
C24 | −0.05484 (7) | 0.4611 (2) | 0.37011 (10) | 0.0308 (4) | |
H24A | −0.0540 | 0.5777 | 0.3666 | 0.037* | |
H24B | −0.0760 | 0.4359 | 0.3751 | 0.037* | |
H24C | −0.0765 | 0.4107 | 0.3204 | 0.037* | |
C25 | 0.02599 (7) | 0.4266 (2) | 0.35538 (9) | 0.0249 (3) | |
H25 | 0.0600 | 0.4375 | 0.3707 | 0.030* | |
C26 | 0.00158 (8) | 0.2545 (2) | 0.32357 (10) | 0.0353 (4) | |
H26A | 0.0334 | 0.1784 | 0.3684 | 0.042* | |
H26B | −0.0097 | 0.2341 | 0.2791 | 0.042* | |
H26C | −0.0345 | 0.2413 | 0.3029 | 0.042* | |
C27 | −0.02368 (8) | 0.5469 (3) | 0.28563 (10) | 0.0382 (5) | |
H27A | −0.0078 | 0.6564 | 0.3063 | 0.046* | |
H27B | −0.0596 | 0.5339 | 0.2653 | 0.046* | |
H27C | −0.0353 | 0.5271 | 0.2408 | 0.046* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Si1 | 0.01359 (19) | 0.0209 (2) | 0.01541 (19) | 0.00036 (15) | 0.01180 (17) | 0.00101 (15) |
O1 | 0.0252 (6) | 0.0377 (7) | 0.0214 (5) | 0.0034 (5) | 0.0206 (5) | 0.0003 (5) |
O2 | 0.0233 (5) | 0.0154 (5) | 0.0166 (5) | 0.0039 (4) | 0.0162 (5) | 0.0030 (4) |
O3 | 0.0357 (6) | 0.0215 (6) | 0.0267 (6) | −0.0029 (5) | 0.0277 (5) | −0.0047 (4) |
O4 | 0.0393 (6) | 0.0213 (6) | 0.0349 (6) | −0.0050 (5) | 0.0342 (6) | −0.0016 (5) |
C1 | 0.0163 (6) | 0.0234 (7) | 0.0148 (6) | −0.0019 (6) | 0.0127 (6) | −0.0005 (5) |
C2 | 0.0156 (6) | 0.0189 (7) | 0.0144 (6) | −0.0024 (5) | 0.0125 (6) | −0.0018 (5) |
C3 | 0.0156 (6) | 0.0145 (7) | 0.0134 (6) | −0.0025 (5) | 0.0119 (6) | −0.0019 (5) |
C4 | 0.0179 (7) | 0.0164 (7) | 0.0151 (6) | 0.0014 (5) | 0.0137 (6) | 0.0007 (5) |
C5 | 0.0198 (7) | 0.0246 (8) | 0.0158 (7) | 0.0015 (6) | 0.0149 (6) | 0.0026 (6) |
C6 | 0.0129 (6) | 0.0188 (7) | 0.0129 (6) | 0.0031 (5) | 0.0105 (6) | 0.0027 (5) |
C7 | 0.0175 (6) | 0.0166 (7) | 0.0166 (6) | 0.0015 (5) | 0.0140 (6) | 0.0022 (5) |
C8 | 0.0191 (7) | 0.0181 (7) | 0.0169 (6) | 0.0025 (5) | 0.0148 (6) | 0.0000 (5) |
C9 | 0.0208 (7) | 0.0236 (8) | 0.0174 (7) | 0.0043 (6) | 0.0167 (6) | 0.0039 (6) |
C10 | 0.0184 (7) | 0.0186 (7) | 0.0188 (7) | 0.0017 (5) | 0.0158 (6) | 0.0034 (5) |
C11 | 0.0190 (7) | 0.0195 (7) | 0.0170 (7) | −0.0011 (5) | 0.0153 (6) | −0.0010 (5) |
C12 | 0.0424 (10) | 0.0223 (8) | 0.0343 (9) | −0.0074 (7) | 0.0328 (9) | −0.0087 (7) |
C13 | 0.0290 (8) | 0.0302 (9) | 0.0269 (8) | −0.0033 (7) | 0.0253 (7) | 0.0012 (6) |
C14 | 0.0263 (8) | 0.0210 (8) | 0.0208 (7) | 0.0051 (6) | 0.0182 (7) | 0.0056 (6) |
C15 | 0.0157 (6) | 0.0201 (7) | 0.0152 (6) | 0.0019 (5) | 0.0123 (6) | 0.0005 (5) |
C16 | 0.0206 (7) | 0.0216 (8) | 0.0209 (7) | −0.0004 (6) | 0.0171 (7) | −0.0030 (6) |
C17 | 0.0223 (7) | 0.0230 (8) | 0.0200 (7) | −0.0025 (6) | 0.0167 (7) | −0.0038 (6) |
C18 | 0.0303 (9) | 0.0297 (9) | 0.0350 (9) | −0.0028 (7) | 0.0279 (8) | −0.0012 (7) |
C19 | 0.0281 (8) | 0.0224 (8) | 0.0327 (8) | 0.0022 (6) | 0.0258 (8) | 0.0034 (6) |
C20 | 0.0494 (11) | 0.0273 (10) | 0.0606 (13) | −0.0089 (8) | 0.0484 (11) | −0.0047 (9) |
C21 | 0.0878 (17) | 0.0259 (10) | 0.0725 (15) | −0.0118 (10) | 0.0728 (15) | −0.0132 (10) |
C22 | 0.0166 (7) | 0.0304 (9) | 0.0206 (7) | −0.0015 (6) | 0.0155 (6) | −0.0009 (6) |
C23 | 0.0285 (8) | 0.0318 (9) | 0.0371 (9) | −0.0053 (7) | 0.0279 (8) | −0.0001 (7) |
C24 | 0.0193 (7) | 0.0450 (10) | 0.0288 (8) | 0.0033 (7) | 0.0201 (7) | 0.0044 (7) |
C25 | 0.0162 (7) | 0.0404 (10) | 0.0163 (7) | 0.0005 (6) | 0.0131 (6) | 0.0019 (6) |
C26 | 0.0277 (9) | 0.0515 (11) | 0.0261 (8) | −0.0100 (8) | 0.0222 (8) | −0.0146 (8) |
C27 | 0.0228 (8) | 0.0643 (13) | 0.0210 (8) | 0.0104 (8) | 0.0170 (8) | 0.0124 (8) |
Si1—C22 | 1.8886 (15) | C15—H15A | 0.9900 |
Si1—C25 | 1.8902 (16) | C15—H15B | 0.9900 |
Si1—C19 | 1.8926 (17) | C16—C17 | 1.529 (2) |
Si1—C2 | 1.8962 (15) | C16—H16A | 0.9900 |
O1—C1 | 1.2161 (17) | C16—H16B | 0.9900 |
O2—C14 | 1.4220 (17) | C17—C18 | 1.516 (5) |
O2—C4 | 1.4299 (17) | C17—H17A | 0.9900 |
O3—C8 | 1.3674 (17) | C17—H17B | 0.9900 |
O3—C12 | 1.4206 (19) | C18—H18A | 0.9800 |
O4—C10 | 1.3630 (17) | C18—H18B | 0.9800 |
O4—C13 | 1.425 (4) | C18—H18C | 0.9800 |
C1—C2 | 1.4905 (19) | C19—C21 | 1.525 (2) |
C1—C5 | 1.511 (2) | C19—C20 | 1.527 (6) |
C2—C3 | 1.351 (4) | C19—H19 | 1.0000 |
C3—C6 | 1.485 (4) | C20—H20A | 0.9800 |
C3—C4 | 1.5366 (19) | C20—H20B | 0.9800 |
C4—C5 | 1.528 (4) | C20—H20C | 0.9800 |
C4—C15 | 1.5384 (19) | C21—H21A | 0.9800 |
C5—H5A | 0.9900 | C21—H21B | 0.9800 |
C5—H5B | 0.9900 | C21—H21C | 0.9800 |
C6—C11 | 1.381 (2) | C22—C24 | 1.536 (2) |
C6—C7 | 1.4057 (19) | C22—C23 | 1.540 (2) |
C7—C8 | 1.380 (2) | C22—H22 | 1.0000 |
C7—H7 | 0.9500 | C23—H23A | 0.9800 |
C8—C9 | 1.396 (2) | C23—H23B | 0.9800 |
C9—C10 | 1.378 (2) | C23—H23C | 0.9800 |
C9—H9 | 0.9500 | C24—H24A | 0.9800 |
C10—C11 | 1.394 (2) | C24—H24B | 0.9800 |
C11—H11 | 0.9500 | C24—H24C | 0.9800 |
C12—H12A | 0.9800 | C25—C26 | 1.536 (2) |
C12—H12B | 0.9800 | C25—C27 | 1.536 (2) |
C12—H12C | 0.9800 | C25—H25 | 1.0000 |
C13—H13A | 0.9800 | C26—H26A | 0.9800 |
C13—H13B | 0.9800 | C26—H26B | 0.9800 |
C13—H13C | 0.9800 | C26—H26C | 0.9800 |
C14—H14A | 0.9800 | C27—H27A | 0.9800 |
C14—H14B | 0.9800 | C27—H27B | 0.9800 |
C14—H14C | 0.9800 | C27—H27C | 0.9800 |
C15—C16 | 1.529 (2) | ||
C22—Si1—C25 | 113.49 (7) | C15—C16—C17 | 113.52 (12) |
C22—Si1—C19 | 108.33 (7) | C15—C16—H16A | 108.9 |
C25—Si1—C19 | 109.11 (7) | C17—C16—H16A | 108.9 |
C22—Si1—C2 | 105.57 (6) | C15—C16—H16B | 108.9 |
C25—Si1—C2 | 109.74 (7) | C17—C16—H16B | 108.9 |
C19—Si1—C2 | 110.56 (7) | H16A—C16—H16B | 107.7 |
C14—O2—C4 | 115.53 (11) | C18—C17—C16 | 113.59 (13) |
C8—O3—C12 | 117.52 (12) | C18—C17—H17A | 108.8 |
C10—O4—C13 | 117.17 (12) | C16—C17—H17A | 108.8 |
O1—C1—C2 | 125.91 (13) | C18—C17—H17B | 108.8 |
O1—C1—C5 | 125.15 (13) | C16—C17—H17B | 108.8 |
C2—C1—C5 | 108.93 (12) | H17A—C17—H17B | 107.7 |
C3—C2—C1 | 106.60 (12) | C17—C18—H18A | 109.5 |
C3—C2—Si1 | 133.35 (11) | C17—C18—H18B | 109.5 |
C1—C2—Si1 | 119.92 (10) | H18A—C18—H18B | 109.5 |
C2—C3—C6 | 127.95 (12) | C17—C18—H18C | 109.5 |
C2—C3—C4 | 113.55 (12) | H18A—C18—H18C | 109.5 |
C6—C3—C4 | 118.40 (11) | H18B—C18—H18C | 109.5 |
O2—C4—C5 | 113.17 (11) | C21—C19—C20 | 109.20 (16) |
O2—C4—C3 | 105.40 (10) | C21—C19—Si1 | 114.66 (12) |
C5—C4—C3 | 102.71 (11) | C20—C19—Si1 | 112.57 (12) |
O2—C4—C15 | 110.85 (11) | C21—C19—H19 | 106.6 |
C5—C4—C15 | 112.62 (11) | C20—C19—H19 | 106.6 |
C3—C4—C15 | 111.59 (11) | Si1—C19—H19 | 106.6 |
C1—C5—C4 | 103.81 (11) | C19—C20—H20A | 109.5 |
C1—C5—H5A | 111.0 | C19—C20—H20B | 109.5 |
C4—C5—H5A | 111.0 | H20A—C20—H20B | 109.5 |
C1—C5—H5B | 111.0 | C19—C20—H20C | 109.5 |
C4—C5—H5B | 111.0 | H20A—C20—H20C | 109.5 |
H5A—C5—H5B | 109.0 | H20B—C20—H20C | 109.5 |
C11—C6—C7 | 120.24 (13) | C19—C21—H21A | 109.5 |
C11—C6—C3 | 119.24 (12) | C19—C21—H21B | 109.5 |
C7—C6—C3 | 120.49 (12) | H21A—C21—H21B | 109.5 |
C8—C7—C6 | 118.83 (13) | C19—C21—H21C | 109.5 |
C8—C7—H7 | 120.6 | H21A—C21—H21C | 109.5 |
C6—C7—H7 | 120.6 | H21B—C21—H21C | 109.5 |
O3—C8—C7 | 124.39 (13) | C24—C22—C23 | 110.32 (13) |
O3—C8—C9 | 114.29 (12) | C24—C22—Si1 | 112.98 (11) |
C7—C8—C9 | 121.32 (13) | C23—C22—Si1 | 115.18 (11) |
C10—C9—C8 | 119.15 (13) | C24—C22—H22 | 105.9 |
C10—C9—H9 | 120.4 | C23—C22—H22 | 105.9 |
C8—C9—H9 | 120.4 | Si1—C22—H22 | 105.9 |
O4—C10—C9 | 124.54 (13) | C22—C23—H23A | 109.5 |
O4—C10—C11 | 114.90 (13) | C22—C23—H23B | 109.5 |
C9—C10—C11 | 120.56 (13) | H23A—C23—H23B | 109.5 |
C6—C11—C10 | 119.91 (13) | C22—C23—H23C | 109.5 |
C6—C11—H11 | 120.0 | H23A—C23—H23C | 109.5 |
C10—C11—H11 | 120.0 | H23B—C23—H23C | 109.5 |
O3—C12—H12A | 109.5 | C22—C24—H24A | 109.5 |
O3—C12—H12B | 109.5 | C22—C24—H24B | 109.5 |
H12A—C12—H12B | 109.5 | H24A—C24—H24B | 109.5 |
O3—C12—H12C | 109.5 | C22—C24—H24C | 109.5 |
H12A—C12—H12C | 109.5 | H24A—C24—H24C | 109.5 |
H12B—C12—H12C | 109.5 | H24B—C24—H24C | 109.5 |
O4—C13—H13A | 109.5 | C26—C25—C27 | 109.87 (14) |
O4—C13—H13B | 109.5 | C26—C25—Si1 | 113.00 (11) |
H13A—C13—H13B | 109.5 | C27—C25—Si1 | 113.70 (12) |
O4—C13—H13C | 109.5 | C26—C25—H25 | 106.6 |
H13A—C13—H13C | 109.5 | C27—C25—H25 | 106.6 |
H13B—C13—H13C | 109.5 | Si1—C25—H25 | 106.6 |
O2—C14—H14A | 109.5 | C25—C26—H26A | 109.5 |
O2—C14—H14B | 109.5 | C25—C26—H26B | 109.5 |
H14A—C14—H14B | 109.5 | H26A—C26—H26B | 109.5 |
O2—C14—H14C | 109.5 | C25—C26—H26C | 109.5 |
H14A—C14—H14C | 109.5 | H26A—C26—H26C | 109.5 |
H14B—C14—H14C | 109.5 | H26B—C26—H26C | 109.5 |
C16—C15—C4 | 115.18 (12) | C25—C27—H27A | 109.5 |
C16—C15—H15A | 108.5 | C25—C27—H27B | 109.5 |
C4—C15—H15A | 108.5 | H27A—C27—H27B | 109.5 |
C16—C15—H15B | 108.5 | C25—C27—H27C | 109.5 |
C4—C15—H15B | 108.5 | H27A—C27—H27C | 109.5 |
H15A—C15—H15B | 107.5 | H27B—C27—H27C | 109.5 |
O1—C1—C2—C3 | 165.05 (14) | C6—C7—C8—O3 | −179.32 (13) |
C5—C1—C2—C3 | −14.12 (16) | C6—C7—C8—C9 | 1.0 (2) |
O1—C1—C2—Si1 | −18.4 (2) | O3—C8—C9—C10 | 179.69 (12) |
C5—C1—C2—Si1 | 162.46 (10) | C7—C8—C9—C10 | −0.6 (2) |
C22—Si1—C2—C3 | 139.93 (15) | C13—O4—C10—C9 | −0.6 (2) |
C25—Si1—C2—C3 | 17.28 (17) | C13—O4—C10—C11 | 179.85 (13) |
C19—Si1—C2—C3 | −103.13 (15) | C8—C9—C10—O4 | −179.59 (13) |
C22—Si1—C2—C1 | −35.56 (13) | C8—C9—C10—C11 | −0.1 (2) |
C25—Si1—C2—C1 | −158.21 (11) | C7—C6—C11—C10 | 0.1 (2) |
C19—Si1—C2—C1 | 81.38 (12) | C3—C6—C11—C10 | 178.29 (13) |
C1—C2—C3—C6 | −175.35 (13) | O4—C10—C11—C6 | 179.88 (12) |
Si1—C2—C3—C6 | 8.7 (2) | C9—C10—C11—C6 | 0.3 (2) |
C1—C2—C3—C4 | 1.09 (16) | O2—C4—C15—C16 | 177.07 (11) |
Si1—C2—C3—C4 | −174.83 (11) | C5—C4—C15—C16 | −55.00 (16) |
C14—O2—C4—C5 | −59.75 (15) | C3—C4—C15—C16 | 59.92 (15) |
C14—O2—C4—C3 | −171.23 (11) | C4—C15—C16—C17 | 171.84 (12) |
C14—O2—C4—C15 | 67.88 (15) | C15—C16—C17—C18 | 64.92 (17) |
C2—C3—C4—O2 | 130.51 (12) | C22—Si1—C19—C21 | 53.07 (15) |
C6—C3—C4—O2 | −52.67 (15) | C25—Si1—C19—C21 | 177.07 (14) |
C2—C3—C4—C5 | 11.79 (15) | C2—Si1—C19—C21 | −62.15 (15) |
C6—C3—C4—C5 | −171.39 (12) | C22—Si1—C19—C20 | 178.71 (12) |
C2—C3—C4—C15 | −109.09 (14) | C25—Si1—C19—C20 | −57.29 (14) |
C6—C3—C4—C15 | 67.72 (15) | C2—Si1—C19—C20 | 63.48 (14) |
O1—C1—C5—C4 | −158.20 (14) | C25—Si1—C22—C24 | −54.04 (14) |
C2—C1—C5—C4 | 20.98 (15) | C19—Si1—C22—C24 | 67.30 (13) |
O2—C4—C5—C1 | −132.07 (12) | C2—Si1—C22—C24 | −174.26 (11) |
C3—C4—C5—C1 | −18.94 (14) | C25—Si1—C22—C23 | 73.98 (13) |
C15—C4—C5—C1 | 101.23 (13) | C19—Si1—C22—C23 | −164.68 (12) |
C2—C3—C6—C11 | 75.56 (19) | C2—Si1—C22—C23 | −46.23 (13) |
C4—C3—C6—C11 | −100.74 (15) | C22—Si1—C25—C26 | −46.17 (13) |
C2—C3—C6—C7 | −106.22 (17) | C19—Si1—C25—C26 | −167.07 (11) |
C4—C3—C6—C7 | 77.48 (16) | C2—Si1—C25—C26 | 71.66 (12) |
C11—C6—C7—C8 | −0.7 (2) | C22—Si1—C25—C27 | 79.96 (13) |
C3—C6—C7—C8 | −178.91 (12) | C19—Si1—C25—C27 | −40.94 (14) |
C12—O3—C8—C7 | 3.8 (2) | C2—Si1—C25—C27 | −162.22 (11) |
C12—O3—C8—C9 | −176.46 (13) |
Experimental details
Crystal data | |
Chemical formula | C27H44O4Si |
Mr | 460.71 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 113 |
a, b, c (Å) | 39.294 (4), 8.3327 (10), 29.274 (3) |
β (°) | 146.207 (8) |
V (Å3) | 5331.1 (15) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.12 |
Crystal size (mm) | 0.26 × 0.24 × 0.10 |
Data collection | |
Diffractometer | Rigaku Saturn diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) |
Tmin, Tmax | 0.961, 0.988 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 32688, 6356, 5271 |
Rint | 0.051 |
(sin θ/λ)max (Å−1) | 0.658 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.049, 0.123, 1.09 |
No. of reflections | 6356 |
No. of parameters | 291 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.29, −0.34 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), CrystalStructure (Rigaku, 2005).
References
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Frontier, A. J. & Collison, C. (2005). Tetrahedron, 61, 7577–7606. CrossRef CAS Google Scholar
Geis, O. & Schmalz, H. G. (1998). Angew. Chem. Int. Ed. 37, 911–914. CrossRef CAS Google Scholar
Li, Z., Moser, W. H., Deng, R. & Sun, L. (2007). J. Org. Chem. 72, 10254–10257. Web of Science CrossRef PubMed CAS Google Scholar
Li, Z., Moser, W. H., Zhang, W., Hua, C. & Sun, L. (2008). J. Organomet. Chem. 693, 361–367. Web of Science CrossRef CAS Google Scholar
Rigaku (2005). CrystalClear (Version 1.36) and CrystalStructure (Version 3.70). Rigaku Americas Corporation, The Woodlands, Texas, USA. Google Scholar
Roberts, S. M., Santoro, M. G. & Sickle, E. S. (2002). J. Chem. Soc. Perkin Trans. 1, pp. 1735–1742. Web of Science CrossRef Google Scholar
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Shi, X., Gorin, D. J. & Toste, F. D. (2005). J. Am. Chem. Soc. 127, 5802–5803. Web of Science CrossRef PubMed CAS Google Scholar
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Cyclopentenones are common structural units in bioactive natural products and useful building blocks. For a review see: (Roberts et al., 2002). While various approaches such as the Nazarov reaction (Frontier & Collison, 2005), Pauson–Khand reaction (Geis & Schmalz, 1998), Rautenstrauch rearrangement reaction (Shi et al., 2005), and intramolecular hydroacylation reaction (Tanaka & Fu, 2001) have been developed for construction of this important ring system. The title molecule was synthesized by [4 + 1] reaction of triisopropylsilyl vinyl ketene with Kobrich reagent (Li et al., 2007; Li et al., 2008).
The molecule structure of C27H44O4Si, is illustrated on Fig.1. The molecule consists of one cyclopentenone (C1–C5) and one phenyl ring (C6–C11). These rings are form the dihedral angle 73.2 (6)°. In the title molecule all bond lengths and bond angles are agree with published (Allen et al., 1987).