Literature DB >> 21580366

4'-Bromo-butyl ent-16-oxobeyeran-19-oate.

Junqing Chen, Xiaoming Zha.   

Abstract

The title compound, C(24)H(37)BrO(3), is a tetra-cyclic diterpenoid with a beyerane skeleton, synthesized by esterification of isosteviol. It comprises a fused four-ring system A/B/C/D. Rings A and B have a chair conformation, whereas ring C is an unsymmetrical distorted chair; the remaining five-membered ring D adopts an envelope conformation. The stereochemistry of the A/B and B/C ring junctions are trans, while the C/D junction is cis.

Entities:  

Year:  2010        PMID： 21580366      PMCID： PMC2983525          DOI： 10.1107/S1600536810005167

Source DB:  PubMed          Journal:  Acta Crystallogr Sect E Struct Rep Online        ISSN： 1600-5368


Related literature

For the pharmacological activity of isosteviol, see: Liu et al. (2001 ▶); Mizushina et al. (2005 ▶); Wong et al. (2004 ▶); Xu et al. (2007 ▶). For ring conformations, see: Cremer & Pople (1975 ▶). For the synthesis of isosteviol derivates via esterification and bromination, see: Cai et al. (2009 ▶); Chen (2010 ▶).

Experimental

Crystal data

C24H37BrO3 M = 453.45 Orthorhombic, a = 7.4335 (10) Å b = 9.7732 (14) Å c = 30.920 (4) Å V = 2246.3 (5) Å3 Z = 4 Mo Kα radiation μ = 1.85 mm−1 T = 298 K 0.45 × 0.43 × 0.37 mm

Data collection

Bruker SMART CCD area-detector diffractometer Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T min = 0.490, T max = 0.548 11802 measured reflections 3955 independent reflections 3041 reflections with I > 2/s(I) R int = 0.052

Refinement

R[F 2 > 2σ(F 2)] = 0.042 wR(F 2) = 0.108 S = 1.00 3955 reflections 256 parameters H-atom parameters constrained Δρmax = 0.64 e Å−3 Δρmin = −0.25 e Å−3 Absolute structure: Flack (1983 ▶), 1657 Friedel pairs Flack parameter: 0.065 (11) Data collection: SMART (Bruker, 1999 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; 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: SHELXTL and PLATON (Spek, 2009 ▶). Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536810005167/bg2330sup1.cif Structure factors: contains datablocks I. DOI: 10.1107/S1600536810005167/bg2330Isup2.hkl Additional supplementary materials: crystallographic information; 3D view; checkCIF report
C24H37BrO3Dx = 1.341 Mg m−3
Mr = 453.45Melting point = 372–373 K
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 3390 reflections
a = 7.4335 (10) Åθ = 2.2–20.1°
b = 9.7732 (14) ŵ = 1.85 mm−1
c = 30.920 (4) ÅT = 298 K
V = 2246.3 (5) Å3Block, colourless
Z = 40.45 × 0.43 × 0.37 mm
F(000) = 960
Bruker SMART CCD area-detector diffractometer3955 independent reflections
Radiation source: fine-focus sealed tube3041 reflections with I > 2/s(I)
graphiteRint = 0.052
phi and ω scansθmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 1999)h = −8→8
Tmin = 0.490, Tmax = 0.548k = −11→11
11802 measured reflectionsl = −25→36
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.108w = 1/[σ2(Fo2) + (0.0392P)2 + 0.9109P] where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max = 0.001
3955 reflectionsΔρmax = 0.64 e Å−3
256 parametersΔρmin = −0.25 e Å−3
0 restraintsAbsolute structure: Flack (1983), 1657 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.065 (11)
Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > σ(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.
xyzUiso*/Ueq
Br11.06095 (7)0.65680 (5)0.843138 (17)0.06872 (19)
O10.6425 (6)1.2658 (4)0.55233 (12)0.0896 (14)
O20.4910 (4)0.6155 (3)0.72346 (9)0.0539 (8)
O30.2689 (5)0.7630 (3)0.71082 (10)0.0596 (8)
C10.3384 (5)0.5981 (4)0.65535 (13)0.0409 (9)
C20.4651 (7)0.4761 (4)0.64746 (13)0.0509 (11)
H2A0.46480.41870.67310.061*
H2B0.41740.42220.62380.061*
C30.6590 (7)0.5144 (4)0.63695 (14)0.0500 (11)
H3A0.71500.55390.66240.060*
H3B0.72540.43240.62930.060*
C40.6691 (6)0.6156 (4)0.59994 (14)0.0465 (10)
H4A0.62810.57100.57370.056*
H4B0.79370.64180.59570.056*
C50.5556 (5)0.7466 (4)0.60725 (11)0.0336 (8)
C60.5564 (5)0.8292 (4)0.56375 (11)0.0348 (8)
H60.52870.76220.54110.042*
C70.7413 (6)0.8882 (4)0.55177 (13)0.0463 (11)
H7A0.78220.94680.57510.056*
H7B0.82650.81360.54900.056*
C80.7401 (6)0.9696 (5)0.51008 (14)0.0522 (11)
H8A0.73560.90630.48590.063*
H8B0.85191.02030.50800.063*
C90.5820 (7)1.0706 (4)0.50609 (13)0.0511 (11)
C100.5754 (7)1.1544 (5)0.54781 (14)0.0539 (11)
C110.4664 (6)1.0794 (4)0.58069 (12)0.0403 (10)
H11A0.36061.13200.58860.048*
H11B0.53691.06270.60650.048*
C120.4113 (5)0.9427 (4)0.55920 (11)0.0355 (9)
C130.2273 (5)0.8911 (4)0.57262 (13)0.0431 (10)
H13A0.18460.82600.55130.052*
H13B0.14370.96730.57320.052*
C140.2291 (5)0.8229 (4)0.61678 (13)0.0401 (9)
H14A0.10900.79170.62400.048*
H14B0.26670.88840.63850.048*
C150.3585 (5)0.7013 (4)0.61649 (12)0.0356 (9)
H150.32370.64820.59090.043*
C160.4094 (6)0.9881 (4)0.51133 (12)0.0454 (10)
H16A0.40900.90940.49220.055*
H16B0.30461.04400.50520.055*
C170.3620 (6)0.6695 (5)0.69846 (13)0.0428 (10)
C180.1425 (6)0.5419 (5)0.65644 (17)0.0630 (13)
H18A0.13400.47030.67760.095*
H18B0.11150.50620.62850.095*
H18C0.06110.61450.66390.095*
C190.6359 (5)0.8274 (4)0.64501 (12)0.0404 (9)
H19A0.64880.76840.66960.061*
H19B0.55750.90210.65220.061*
H19C0.75160.86250.63680.061*
C200.5970 (8)1.1571 (5)0.46522 (16)0.0774 (16)
H20A0.59841.09840.44030.116*
H20B0.70611.20960.46610.116*
H20C0.49581.21790.46350.116*
C210.5242 (7)0.6883 (5)0.76431 (14)0.0647 (14)
H21A0.41630.68790.78200.078*
H21B0.55700.78260.75850.078*
C220.6719 (6)0.6183 (5)0.78729 (15)0.0587 (12)
H22A0.63830.52340.79170.070*
H22B0.68570.65990.81560.070*
C230.8505 (7)0.6223 (7)0.76451 (16)0.0757 (16)
H23A0.83860.57750.73670.091*
H23B0.88290.71700.75920.091*
C240.9989 (7)0.5548 (6)0.78940 (17)0.0716 (15)
H24A1.10490.54840.77120.086*
H24B0.96260.46250.79700.086*
U11U22U33U12U13U23
Br10.0692 (3)0.0608 (3)0.0761 (3)0.0049 (3)−0.0274 (3)−0.0054 (3)
O10.135 (4)0.054 (2)0.080 (3)−0.039 (2)0.034 (2)−0.0121 (19)
O20.060 (2)0.0612 (19)0.0409 (16)0.0070 (15)−0.0069 (14)−0.0048 (14)
O30.070 (2)0.062 (2)0.0470 (18)0.0160 (19)0.0007 (16)−0.0034 (16)
C10.046 (2)0.040 (2)0.037 (2)−0.0072 (18)−0.004 (2)0.0044 (19)
C20.076 (3)0.034 (2)0.043 (3)0.002 (2)−0.008 (2)0.0040 (18)
C30.062 (3)0.041 (2)0.047 (3)0.016 (2)−0.003 (2)0.003 (2)
C40.043 (2)0.050 (3)0.047 (2)0.011 (2)−0.0043 (19)−0.005 (2)
C50.032 (2)0.0344 (19)0.035 (2)−0.0022 (19)−0.0021 (18)−0.0015 (16)
C60.037 (2)0.0328 (18)0.0346 (19)−0.004 (2)0.0010 (17)−0.0038 (16)
C70.040 (2)0.046 (2)0.053 (3)−0.0039 (19)0.009 (2)−0.006 (2)
C80.053 (3)0.057 (3)0.047 (3)−0.006 (2)0.015 (2)−0.004 (2)
C90.073 (3)0.043 (2)0.037 (2)−0.007 (2)0.009 (2)0.0028 (18)
C100.068 (3)0.039 (2)0.054 (3)−0.006 (3)0.010 (2)−0.002 (2)
C110.048 (3)0.034 (2)0.039 (2)0.0043 (19)0.0012 (19)0.0017 (17)
C120.041 (2)0.038 (2)0.0273 (19)−0.0003 (18)−0.0034 (17)0.0009 (16)
C130.037 (2)0.045 (2)0.047 (2)0.0042 (18)−0.0059 (18)0.007 (2)
C140.029 (2)0.046 (2)0.046 (2)−0.0009 (19)0.0018 (17)0.004 (2)
C150.037 (2)0.039 (2)0.031 (2)−0.0041 (17)−0.0016 (17)−0.0046 (16)
C160.057 (3)0.045 (2)0.035 (2)−0.001 (2)−0.006 (2)0.0011 (18)
C170.044 (2)0.044 (2)0.041 (2)−0.005 (2)−0.0008 (18)0.009 (2)
C180.061 (3)0.069 (3)0.059 (3)−0.029 (2)−0.005 (3)0.009 (3)
C190.037 (2)0.047 (2)0.037 (2)−0.0021 (18)−0.0049 (16)−0.003 (2)
C200.108 (5)0.065 (3)0.060 (3)−0.013 (4)0.020 (3)0.018 (3)
C210.075 (3)0.082 (4)0.037 (2)−0.001 (3)−0.012 (2)−0.006 (2)
C220.059 (3)0.069 (3)0.048 (3)−0.004 (2)−0.004 (2)0.000 (2)
C230.064 (3)0.111 (5)0.052 (3)−0.003 (3)−0.001 (2)0.009 (3)
C240.056 (3)0.091 (4)0.068 (3)−0.004 (3)−0.004 (3)−0.016 (3)
Br1—C241.992 (5)C11—C121.547 (5)
O1—C101.206 (5)C11—H11A0.9700
O2—C171.340 (5)C11—H11B0.9700
O2—C211.470 (5)C12—C131.516 (6)
O3—C171.208 (5)C12—C161.545 (5)
C1—C171.515 (6)C13—C141.519 (5)
C1—C21.539 (6)C13—H13A0.9700
C1—C181.557 (6)C13—H13B0.9700
C1—C151.576 (5)C14—C151.529 (5)
C2—C31.524 (6)C14—H14A0.9700
C2—H2A0.9700C14—H14B0.9700
C2—H2B0.9700C15—H150.9800
C3—C41.515 (6)C16—H16A0.9700
C3—H3A0.9700C16—H16B0.9700
C3—H3B0.9700C18—H18A0.9600
C4—C51.549 (5)C18—H18B0.9600
C4—H4A0.9700C18—H18C0.9600
C4—H4B0.9700C19—H19A0.9600
C5—C191.531 (5)C19—H19B0.9600
C5—C151.557 (5)C19—H19C0.9600
C5—C61.569 (5)C20—H20A0.9600
C6—C71.535 (6)C20—H20B0.9600
C6—C121.554 (5)C20—H20C0.9600
C6—H60.9800C21—C221.476 (7)
C7—C81.515 (6)C21—H21A0.9700
C7—H7A0.9700C21—H21B0.9700
C7—H7B0.9700C22—C231.503 (7)
C8—C91.540 (7)C22—H22A0.9700
C8—H8A0.9700C22—H22B0.9700
C8—H8B0.9700C23—C241.499 (7)
C9—C161.524 (6)C23—H23A0.9700
C9—C201.525 (6)C23—H23B0.9700
C9—C101.529 (6)C24—H24A0.9700
C10—C111.492 (6)C24—H24B0.9700
C17—O2—C21115.1 (3)C12—C13—C14112.6 (3)
C17—C1—C2115.2 (3)C12—C13—H13A109.1
C17—C1—C18104.6 (4)C14—C13—H13A109.1
C2—C1—C18107.6 (3)C12—C13—H13B109.1
C17—C1—C15111.4 (3)C14—C13—H13B109.1
C2—C1—C15108.5 (3)H13A—C13—H13B107.8
C18—C1—C15109.3 (3)C13—C14—C15110.0 (3)
C3—C2—C1115.0 (3)C13—C14—H14A109.7
C3—C2—H2A108.5C15—C14—H14A109.7
C1—C2—H2A108.5C13—C14—H14B109.7
C3—C2—H2B108.5C15—C14—H14B109.7
C1—C2—H2B108.5H14A—C14—H14B108.2
H2A—C2—H2B107.5C14—C15—C5111.8 (3)
C4—C3—C2111.6 (4)C14—C15—C1115.7 (3)
C4—C3—H3A109.3C5—C15—C1114.3 (3)
C2—C3—H3A109.3C14—C15—H15104.5
C4—C3—H3B109.3C5—C15—H15104.5
C2—C3—H3B109.3C1—C15—H15104.5
H3A—C3—H3B108.0C9—C16—C12104.2 (3)
C3—C4—C5113.8 (3)C9—C16—H16A110.9
C3—C4—H4A108.8C12—C16—H16A110.9
C5—C4—H4A108.8C9—C16—H16B110.9
C3—C4—H4B108.8C12—C16—H16B110.9
C5—C4—H4B108.8H16A—C16—H16B108.9
H4A—C4—H4B107.7O3—C17—O2121.7 (4)
C19—C5—C4109.0 (3)O3—C17—C1124.1 (4)
C19—C5—C15111.9 (3)O2—C17—C1114.1 (4)
C4—C5—C15107.7 (3)C1—C18—H18A109.5
C19—C5—C6112.8 (3)C1—C18—H18B109.5
C4—C5—C6107.3 (3)H18A—C18—H18B109.5
C15—C5—C6107.9 (3)C1—C18—H18C109.5
C7—C6—C12109.4 (3)H18A—C18—H18C109.5
C7—C6—C5113.8 (3)H18B—C18—H18C109.5
C12—C6—C5116.3 (3)C5—C19—H19A109.5
C7—C6—H6105.5C5—C19—H19B109.5
C12—C6—H6105.5H19A—C19—H19B109.5
C5—C6—H6105.5C5—C19—H19C109.5
C8—C7—C6113.4 (4)H19A—C19—H19C109.5
C8—C7—H7A108.9H19B—C19—H19C109.5
C6—C7—H7A108.9C9—C20—H20A109.5
C8—C7—H7B108.9C9—C20—H20B109.5
C6—C7—H7B108.9H20A—C20—H20B109.5
H7A—C7—H7B107.7C9—C20—H20C109.5
C7—C8—C9114.1 (3)H20A—C20—H20C109.5
C7—C8—H8A108.7H20B—C20—H20C109.5
C9—C8—H8A108.7O2—C21—C22108.3 (4)
C7—C8—H8B108.7O2—C21—H21A110.0
C9—C8—H8B108.7C22—C21—H21A110.0
H8A—C8—H8B107.6O2—C21—H21B110.0
C16—C9—C20116.3 (4)C22—C21—H21B110.0
C16—C9—C1099.6 (3)H21A—C21—H21B108.4
C20—C9—C10113.8 (3)C21—C22—C23114.8 (4)
C16—C9—C8107.2 (3)C21—C22—H22A108.6
C20—C9—C8111.5 (4)C23—C22—H22A108.6
C10—C9—C8107.5 (4)C21—C22—H22B108.6
O1—C10—C11126.1 (4)C23—C22—H22B108.6
O1—C10—C9124.6 (4)H22A—C22—H22B107.5
C11—C10—C9109.2 (4)C24—C23—C22113.5 (4)
C10—C11—C12106.0 (3)C24—C23—H23A108.9
C10—C11—H11A110.5C22—C23—H23A108.9
C12—C11—H11A110.5C24—C23—H23B108.9
C10—C11—H11B110.5C22—C23—H23B108.9
C12—C11—H11B110.5H23A—C23—H23B107.7
H11A—C11—H11B108.7C23—C24—Br1112.2 (4)
C13—C12—C16110.4 (3)C23—C24—H24A109.2
C13—C12—C11114.1 (3)Br1—C24—H24A109.2
C16—C12—C1199.6 (3)C23—C24—H24B109.2
C13—C12—C6111.3 (3)Br1—C24—H24B109.2
C16—C12—C6107.3 (3)H24A—C24—H24B107.9
C11—C12—C6113.2 (3)
  6 in total

1.  A short history of SHELX.

Authors:  George M Sheldrick
Journal:  Acta Crystallogr A       Date:  2007-12-21       Impact factor: 2.290

2.  The cardioprotective effect of isosteviol on rats with heart ischemia-reperfusion injury.

Authors:  Deyi Xu; Yongfang Li; Jiping Wang; Andrew K Davey; Shuangjie Zhang; Allan M Evans
Journal:  Life Sci       Date:  2006-09-16       Impact factor: 5.037

3.  Structural analysis of isosteviol and related compounds as DNA polymerase and DNA topoisomerase inhibitors.

Authors:  Yoshiyuki Mizushina; Toshihiro Akihisa; Motohiko Ukiya; Yusuke Hamasaki; Chikako Murakami-Nakai; Isoko Kuriyama; Toshifumi Takeuchi; Fumio Sugawara; Hiromi Yoshida
Journal:  Life Sci       Date:  2005-09-09       Impact factor: 5.037

4.  Isopropyl ent-15α-bromo-16-oxo-beyeran-19-oate.

Authors:  Junqing Chen
Journal:  Acta Crystallogr Sect E Struct Rep Online       Date:  2010-01-23

5.  Isosteviol acts on potassium channels to relax isolated aortic strips of Wistar rat.

Authors:  Kar-Lok Wong; Paul Chan; Hung-Yu Yang; Feng-Lin Hsu; I-Min Liu; Yu-Wan Cheng; Juei-Tang Cheng
Journal:  Life Sci       Date:  2004-03-26       Impact factor: 5.037

6.  Structure validation in chemical crystallography.

Authors:  Anthony L Spek
Journal:  Acta Crystallogr D Biol Crystallogr       Date:  2009-01-20
  6 in total

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