The natural compound (1S,4S,5S,6R,7R,8R,9R,10S)-6-acetoxy-4,9,10-trihydroxy-2,2,5a,9-tetramethyloctahydro-2H-3,9a-methanobenzo[b]oxepin-5-yl furan-3-carboxylate, C22H30O9, (I), is a β-agarofuran sesquiterpene isolated from the seeds of Maytenus boaria as part of a study of the secondary metabolites from Chilean flora. The compound presents a central structure formed by a decalin system esterified with acetate at site 1 and furan-3-carboxylate at site 9. The chirality of the skeleton can be described as 1S,4S,5S,6R,7R,8R,9R,10S, which is consistent with that suggested by NMR studies. Unlike previously reported structures of sesquiterpenes containing a pure dihydro-β-agarofuran skeleton, (I) exhibits a three-dimensional hydrogen-bonded network.
Supporting information
CCDC reference: 1548206
Data collection: CrysAlis PRO (Oxford Diffraction, 2009); cell refinement: CrysAlis PRO (Oxford Diffraction, 2009); data reduction: CrysAlis PRO (Oxford Diffraction, 2009); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015) and PLATON (Spek, 2009).
(1
S,4
S,5
S,6
R,7
R,8
R,9
R,10
S)-6-Acetoxy-4,9,10-trihydroxy-2,2,5a,9-tetramethyloctahydro-2
H-3,9a-methanobenzo[
b]oxepin-5-yl furan-3-carboxylate
top
Crystal data top
C22H30O9 | Dx = 1.366 Mg m−3 |
Mr = 438.46 | Cu Kα radiation, λ = 1.54178 Å |
Orthorhombic, P212121 | Cell parameters from 5831 reflections |
a = 9.1605 (3) Å | θ = 4.1–71.9° |
b = 13.8069 (5) Å | µ = 0.89 mm−1 |
c = 16.8625 (7) Å | T = 295 K |
V = 2132.74 (14) Å3 | Prisms, colourless |
Z = 4 | 0.40 × 0.20 × 0.20 mm |
F(000) = 936 | |
Data collection top
Oxford Diffraction Gemini CCD S Ultra diffractometer | 3781 reflections with I > 2σ(I) |
ω scans, thick slices | Rint = 0.087 |
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009) | θmax = 71.9°, θmin = 4.1° |
Tmin = 0.78, Tmax = 0.83 | h = −9→11 |
17785 measured reflections | k = −16→17 |
4153 independent reflections | l = −20→20 |
Refinement top
Refinement on F2 | Hydrogen site location: mixed |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.061 | w = 1/[σ2(Fo2) + (0.1311P)2] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.165 | (Δ/σ)max < 0.001 |
S = 1.03 | Δρmax = 0.28 e Å−3 |
4153 reflections | Δρmin = −0.30 e Å−3 |
295 parameters | Absolute structure: Flack x determined using 1547 quotients [(I+)-(I-)]/[(I+)+(I-)]
(Parsons et al., 2013) |
3 restraints | Absolute structure parameter: 0.18 (15) |
Special details top
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
O1 | 0.0991 (2) | 0.28072 (15) | 0.15650 (13) | 0.0392 (5) | |
O2 | 0.1561 (3) | 0.09415 (17) | 0.17624 (18) | 0.0538 (6) | |
H2 | 0.090 (4) | 0.117 (3) | 0.146 (2) | 0.065* | |
O3 | 0.2575 (4) | 0.4631 (2) | 0.33803 (15) | 0.0640 (7) | |
H3 | 0.210 (5) | 0.489 (4) | 0.376 (2) | 0.077* | |
O1A | 0.1462 (4) | 0.1811 (2) | 0.32412 (18) | 0.0645 (7) | |
H1A | 0.139 (7) | 0.135 (3) | 0.291 (3) | 0.077* | |
O1B | 0.2037 (2) | 0.48421 (15) | 0.13053 (13) | 0.0408 (5) | |
O2B | 0.3398 (3) | 0.62082 (17) | 0.13775 (17) | 0.0560 (6) | |
O3B | −0.0276 (4) | 0.6172 (3) | −0.0462 (2) | 0.0771 (12) | 0.83 (2) |
C4B' | −0.0276 (4) | 0.6172 (3) | −0.0462 (2) | 0.0771 (12) | 0.17 (2) |
H4B' | −0.1063 | 0.5997 | −0.0781 | 0.093* | 0.17 (2) |
O1C | 0.4858 (3) | 0.41320 (16) | 0.07259 (15) | 0.0484 (6) | |
O2C | 0.4060 (4) | 0.4272 (3) | −0.05184 (18) | 0.0739 (9) | |
C1 | 0.3791 (3) | 0.3366 (2) | 0.08843 (18) | 0.0389 (6) | |
H1 | 0.2895 | 0.3505 | 0.0588 | 0.047* | |
C2 | 0.4377 (4) | 0.2392 (2) | 0.0626 (2) | 0.0491 (7) | |
H2A | 0.5263 | 0.2241 | 0.0915 | 0.059* | |
H2B | 0.4604 | 0.2404 | 0.0064 | 0.059* | |
C3 | 0.3216 (4) | 0.1626 (2) | 0.0793 (2) | 0.0497 (8) | |
H3C | 0.3574 | 0.0999 | 0.0622 | 0.060* | |
H3D | 0.2347 | 0.1774 | 0.0487 | 0.060* | |
C4 | 0.2810 (3) | 0.1571 (2) | 0.1676 (2) | 0.0426 (7) | |
C5 | 0.2342 (3) | 0.2595 (2) | 0.19809 (17) | 0.0355 (6) | |
C6 | 0.1984 (4) | 0.2669 (2) | 0.2867 (2) | 0.0458 (7) | |
H6 | 0.2846 | 0.2904 | 0.3153 | 0.055* | |
C7 | 0.0840 (4) | 0.3485 (3) | 0.2825 (2) | 0.0488 (7) | |
H7 | 0.0258 | 0.3514 | 0.3312 | 0.059* | |
C8 | 0.1700 (4) | 0.4435 (3) | 0.2697 (2) | 0.0478 (7) | |
H8 | 0.1005 | 0.4967 | 0.2624 | 0.057* | |
C9 | 0.2780 (3) | 0.4425 (2) | 0.19852 (18) | 0.0385 (6) | |
H9 | 0.3587 | 0.4860 | 0.2121 | 0.046* | |
C10 | 0.3460 (3) | 0.34241 (19) | 0.17802 (17) | 0.0346 (6) | |
C11 | −0.0103 (3) | 0.3193 (2) | 0.2112 (2) | 0.0472 (7) | |
C12 | −0.1211 (4) | 0.2400 (3) | 0.2310 (3) | 0.0670 (11) | |
H12A | −0.1601 | 0.2136 | 0.1828 | 0.100* | |
H12B | −0.1990 | 0.2671 | 0.2621 | 0.100* | |
H12C | −0.0739 | 0.1896 | 0.2607 | 0.100* | |
C13 | −0.0947 (4) | 0.4001 (3) | 0.1708 (3) | 0.0580 (9) | |
H13A | −0.0277 | 0.4482 | 0.1517 | 0.087* | |
H13B | −0.1607 | 0.4291 | 0.2081 | 0.087* | |
H13C | −0.1490 | 0.3740 | 0.1271 | 0.087* | |
C14 | 0.4011 (4) | 0.1066 (3) | 0.2149 (3) | 0.0602 (10) | |
H14A | 0.3830 | 0.1148 | 0.2706 | 0.090* | |
H14B | 0.4939 | 0.1345 | 0.2016 | 0.090* | |
H14C | 0.4017 | 0.0389 | 0.2022 | 0.090* | |
C15 | 0.4883 (3) | 0.3359 (2) | 0.2259 (2) | 0.0453 (7) | |
H15A | 0.5218 | 0.2700 | 0.2267 | 0.068* | |
H15B | 0.4709 | 0.3573 | 0.2793 | 0.068* | |
H15C | 0.5612 | 0.3762 | 0.2018 | 0.068* | |
C1B | 0.2426 (3) | 0.5752 (2) | 0.10788 (18) | 0.0388 (6) | |
C2B | 0.1491 (4) | 0.6089 (2) | 0.04364 (19) | 0.0419 (6) | |
C3B | 0.0408 (5) | 0.5613 (3) | 0.0076 (3) | 0.0688 (11) | |
H3B | 0.0158 | 0.4974 | 0.0183 | 0.083* | |
C4B | 0.0417 (5) | 0.7046 (3) | −0.0446 (2) | 0.0652 (12) | 0.83 (2) |
H4B | 0.0173 | 0.7576 | −0.0759 | 0.078* | 0.83 (2) |
O3B' | 0.0417 (5) | 0.7046 (3) | −0.0446 (2) | 0.0652 (12) | 0.17 (2) |
C5B | 0.1493 (5) | 0.7029 (3) | 0.0085 (3) | 0.0591 (9) | |
H5B | 0.2127 | 0.7535 | 0.0204 | 0.071* | |
C1C | 0.4837 (4) | 0.4543 (3) | 0.0021 (2) | 0.0533 (8) | |
C2C | 0.5879 (6) | 0.5372 (3) | −0.0036 (3) | 0.0787 (14) | |
H2CA | 0.6419 | 0.5326 | −0.0523 | 0.118* | |
H2CB | 0.6542 | 0.5353 | 0.0404 | 0.118* | |
H2CC | 0.5346 | 0.5971 | −0.0027 | 0.118* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1 | 0.0248 (9) | 0.0422 (10) | 0.0505 (11) | 0.0010 (8) | −0.0022 (8) | 0.0009 (8) |
O2 | 0.0454 (13) | 0.0396 (11) | 0.0762 (16) | −0.0092 (10) | −0.0052 (12) | 0.0096 (11) |
O3 | 0.0690 (17) | 0.0729 (16) | 0.0502 (14) | 0.0021 (14) | 0.0003 (13) | −0.0198 (12) |
O1A | 0.0740 (18) | 0.0571 (15) | 0.0625 (15) | −0.0053 (13) | 0.0129 (15) | 0.0209 (12) |
O1B | 0.0363 (10) | 0.0333 (9) | 0.0529 (11) | −0.0017 (7) | −0.0077 (9) | 0.0044 (8) |
O2B | 0.0496 (13) | 0.0430 (12) | 0.0754 (16) | −0.0118 (10) | −0.0124 (12) | 0.0046 (11) |
O3B | 0.072 (2) | 0.086 (2) | 0.073 (2) | −0.0075 (18) | −0.0261 (17) | 0.0179 (17) |
C4B' | 0.072 (2) | 0.086 (2) | 0.073 (2) | −0.0075 (18) | −0.0261 (17) | 0.0179 (17) |
O1C | 0.0415 (12) | 0.0480 (12) | 0.0558 (13) | −0.0083 (10) | 0.0079 (10) | 0.0055 (10) |
O2C | 0.077 (2) | 0.085 (2) | 0.0600 (16) | 0.0002 (17) | 0.0053 (15) | 0.0227 (15) |
C1 | 0.0336 (14) | 0.0389 (14) | 0.0443 (15) | −0.0018 (11) | 0.0041 (11) | 0.0026 (11) |
C2 | 0.0445 (16) | 0.0458 (16) | 0.0571 (18) | 0.0020 (13) | 0.0101 (14) | −0.0044 (14) |
C3 | 0.0483 (18) | 0.0406 (15) | 0.0602 (19) | 0.0021 (13) | 0.0023 (15) | −0.0086 (14) |
C4 | 0.0353 (14) | 0.0322 (12) | 0.0602 (18) | 0.0005 (11) | −0.0034 (13) | 0.0033 (12) |
C5 | 0.0290 (12) | 0.0330 (13) | 0.0447 (14) | 0.0009 (10) | −0.0023 (10) | 0.0036 (10) |
C6 | 0.0454 (16) | 0.0452 (16) | 0.0466 (16) | 0.0004 (13) | 0.0033 (13) | 0.0079 (12) |
C7 | 0.0429 (16) | 0.0543 (17) | 0.0494 (16) | 0.0030 (15) | 0.0112 (13) | −0.0008 (14) |
C8 | 0.0462 (16) | 0.0480 (16) | 0.0490 (16) | 0.0029 (14) | 0.0075 (13) | −0.0085 (13) |
C9 | 0.0353 (14) | 0.0362 (13) | 0.0440 (15) | 0.0011 (11) | −0.0028 (11) | −0.0007 (11) |
C10 | 0.0274 (12) | 0.0340 (12) | 0.0426 (13) | −0.0018 (10) | −0.0017 (11) | 0.0020 (10) |
C11 | 0.0277 (13) | 0.0498 (17) | 0.064 (2) | 0.0011 (12) | 0.0080 (13) | 0.0021 (14) |
C12 | 0.0377 (17) | 0.066 (2) | 0.097 (3) | −0.0071 (16) | 0.0127 (19) | 0.012 (2) |
C13 | 0.0305 (15) | 0.0557 (18) | 0.088 (3) | 0.0086 (13) | 0.0011 (16) | 0.0020 (18) |
C14 | 0.052 (2) | 0.0444 (17) | 0.085 (3) | 0.0089 (16) | −0.0139 (19) | 0.0130 (17) |
C15 | 0.0337 (14) | 0.0467 (16) | 0.0556 (17) | −0.0020 (12) | −0.0092 (13) | 0.0030 (13) |
C1B | 0.0340 (14) | 0.0345 (13) | 0.0479 (15) | 0.0018 (11) | 0.0040 (12) | −0.0011 (10) |
C2B | 0.0393 (15) | 0.0390 (14) | 0.0475 (15) | 0.0069 (12) | −0.0007 (12) | 0.0025 (11) |
C3B | 0.073 (3) | 0.061 (2) | 0.073 (3) | −0.017 (2) | −0.024 (2) | 0.0168 (19) |
C4B | 0.071 (2) | 0.061 (2) | 0.064 (2) | 0.0169 (18) | −0.0047 (18) | 0.0123 (16) |
O3B' | 0.071 (2) | 0.061 (2) | 0.064 (2) | 0.0169 (18) | −0.0047 (18) | 0.0123 (16) |
C5B | 0.060 (2) | 0.0451 (18) | 0.072 (2) | 0.0044 (16) | −0.0056 (19) | 0.0109 (16) |
C1C | 0.056 (2) | 0.0459 (17) | 0.058 (2) | 0.0070 (15) | 0.0199 (17) | 0.0048 (15) |
C2C | 0.096 (4) | 0.051 (2) | 0.089 (3) | −0.011 (2) | 0.037 (3) | 0.008 (2) |
Geometric parameters (Å, º) top
O1—C5 | 1.453 (3) | C7—C11 | 1.534 (5) |
O1—C11 | 1.463 (4) | C7—C8 | 1.544 (5) |
O2—C4 | 1.445 (4) | C7—H7 | 0.9800 |
O2—H2 | 0.854 (14) | C8—C9 | 1.555 (4) |
O3—C8 | 1.430 (4) | C8—H8 | 0.9800 |
O3—H3 | 0.848 (14) | C9—C10 | 1.555 (4) |
O1A—C6 | 1.424 (4) | C9—H9 | 0.9800 |
O1A—H1A | 0.851 (14) | C10—C15 | 1.536 (4) |
O1B—C1B | 1.360 (4) | C11—C13 | 1.518 (5) |
O1B—C9 | 1.452 (4) | C11—C12 | 1.530 (5) |
O2B—C1B | 1.201 (4) | C12—H12A | 0.9600 |
O3B—C3B | 1.346 (5) | C12—H12B | 0.9600 |
O3B—C4B | 1.364 (6) | C12—H12C | 0.9600 |
C4B'—C3B | 1.346 (5) | C13—H13A | 0.9600 |
C4B'—O3B' | 1.364 (6) | C13—H13B | 0.9600 |
C4B'—H4B' | 0.9300 | C13—H13C | 0.9600 |
O1C—C1C | 1.318 (5) | C14—H14A | 0.9600 |
O1C—C1 | 1.465 (3) | C14—H14B | 0.9600 |
O2C—C1C | 1.214 (6) | C14—H14C | 0.9600 |
C1—C2 | 1.512 (4) | C15—H15A | 0.9600 |
C1—C10 | 1.543 (4) | C15—H15B | 0.9600 |
C1—H1 | 0.9800 | C15—H15C | 0.9600 |
C2—C3 | 1.526 (5) | C1B—C2B | 1.458 (4) |
C2—H2A | 0.9700 | C2B—C3B | 1.336 (5) |
C2—H2B | 0.9700 | C2B—C5B | 1.427 (5) |
C3—C4 | 1.535 (5) | C3B—H3B | 0.9300 |
C3—H3C | 0.9700 | C4B—C5B | 1.331 (6) |
C3—H3D | 0.9700 | C4B—H4B | 0.9300 |
C4—C14 | 1.527 (5) | O3B'—C5B | 1.331 (6) |
C4—C5 | 1.564 (4) | C5B—H5B | 0.9300 |
C5—C6 | 1.534 (4) | C1C—C2C | 1.493 (6) |
C5—C10 | 1.573 (4) | C2C—H2CA | 0.9600 |
C6—C7 | 1.541 (5) | C2C—H2CB | 0.9600 |
C6—H6 | 0.9800 | C2C—H2CC | 0.9600 |
| | | |
C5—O1—C11 | 110.7 (2) | C15—C10—C1 | 110.2 (2) |
C4—O2—H2 | 107 (3) | C15—C10—C9 | 106.0 (2) |
C8—O3—H3 | 113 (4) | C1—C10—C9 | 110.0 (2) |
C6—O1A—H1A | 111 (4) | C15—C10—C5 | 113.4 (2) |
C1B—O1B—C9 | 117.7 (2) | C1—C10—C5 | 107.5 (2) |
C3B—O3B—C4B | 106.0 (3) | C9—C10—C5 | 109.8 (2) |
C3B—C4B'—O3B' | 106.0 (3) | O1—C11—C13 | 109.5 (3) |
C3B—C4B'—H4B' | 127.0 | O1—C11—C12 | 109.4 (3) |
O3B'—C4B'—H4B' | 127.0 | C13—C11—C12 | 106.6 (3) |
C1C—O1C—C1 | 117.8 (3) | O1—C11—C7 | 101.8 (2) |
O1C—C1—C2 | 110.7 (2) | C13—C11—C7 | 116.4 (3) |
O1C—C1—C10 | 105.8 (2) | C12—C11—C7 | 113.0 (3) |
C2—C1—C10 | 113.5 (2) | C11—C12—H12A | 109.5 |
O1C—C1—H1 | 108.9 | C11—C12—H12B | 109.5 |
C2—C1—H1 | 108.9 | H12A—C12—H12B | 109.5 |
C10—C1—H1 | 108.9 | C11—C12—H12C | 109.5 |
C1—C2—C3 | 108.4 (3) | H12A—C12—H12C | 109.5 |
C1—C2—H2A | 110.0 | H12B—C12—H12C | 109.5 |
C3—C2—H2A | 110.0 | C11—C13—H13A | 109.5 |
C1—C2—H2B | 110.0 | C11—C13—H13B | 109.5 |
C3—C2—H2B | 110.0 | H13A—C13—H13B | 109.5 |
H2A—C2—H2B | 108.4 | C11—C13—H13C | 109.5 |
C2—C3—C4 | 112.4 (3) | H13A—C13—H13C | 109.5 |
C2—C3—H3C | 109.1 | H13B—C13—H13C | 109.5 |
C4—C3—H3C | 109.1 | C4—C14—H14A | 109.5 |
C2—C3—H3D | 109.1 | C4—C14—H14B | 109.5 |
C4—C3—H3D | 109.1 | H14A—C14—H14B | 109.5 |
H3C—C3—H3D | 107.8 | C4—C14—H14C | 109.5 |
O2—C4—C14 | 104.0 (3) | H14A—C14—H14C | 109.5 |
O2—C4—C3 | 108.6 (3) | H14B—C14—H14C | 109.5 |
C14—C4—C3 | 110.8 (3) | C10—C15—H15A | 109.5 |
O2—C4—C5 | 107.1 (2) | C10—C15—H15B | 109.5 |
C14—C4—C5 | 116.0 (3) | H15A—C15—H15B | 109.5 |
C3—C4—C5 | 109.9 (2) | C10—C15—H15C | 109.5 |
O1—C5—C6 | 105.9 (2) | H15A—C15—H15C | 109.5 |
O1—C5—C4 | 104.9 (2) | H15B—C15—H15C | 109.5 |
C6—C5—C4 | 116.1 (2) | O2B—C1B—O1B | 124.1 (3) |
O1—C5—C10 | 107.7 (2) | O2B—C1B—C2B | 125.4 (3) |
C6—C5—C10 | 107.5 (2) | O1B—C1B—C2B | 110.5 (3) |
C4—C5—C10 | 114.1 (2) | C3B—C2B—C5B | 105.0 (3) |
O1A—C6—C5 | 116.6 (3) | C3B—C2B—C1B | 128.2 (3) |
O1A—C6—C7 | 113.6 (3) | C5B—C2B—C1B | 126.8 (3) |
C5—C6—C7 | 98.6 (2) | C2B—C3B—O3B | 111.8 (4) |
O1A—C6—H6 | 109.2 | C2B—C3B—C4B' | 111.8 (4) |
C5—C6—H6 | 109.2 | C2B—C3B—H3B | 124.1 |
C7—C6—H6 | 109.2 | O3B—C3B—H3B | 124.1 |
C11—C7—C6 | 103.1 (3) | C5B—C4B—O3B | 110.1 (3) |
C11—C7—C8 | 113.6 (3) | C5B—C4B—H4B | 125.0 |
C6—C7—C8 | 106.3 (3) | O3B—C4B—H4B | 125.0 |
C11—C7—H7 | 111.1 | C5B—O3B'—C4B' | 110.1 (3) |
C6—C7—H7 | 111.1 | O3B'—C5B—C2B | 107.1 (4) |
C8—C7—H7 | 111.1 | C4B—C5B—C2B | 107.1 (4) |
O3—C8—C7 | 109.5 (3) | C4B—C5B—H5B | 126.4 |
O3—C8—C9 | 105.5 (3) | C2B—C5B—H5B | 126.4 |
C7—C8—C9 | 115.1 (3) | O2C—C1C—O1C | 123.5 (4) |
O3—C8—H8 | 108.8 | O2C—C1C—C2C | 124.3 (4) |
C7—C8—H8 | 108.8 | O1C—C1C—C2C | 112.3 (4) |
C9—C8—H8 | 108.8 | C1C—C2C—H2CA | 109.5 |
O1B—C9—C10 | 111.4 (2) | C1C—C2C—H2CB | 109.5 |
O1B—C9—C8 | 107.9 (2) | H2CA—C2C—H2CB | 109.5 |
C10—C9—C8 | 115.7 (3) | C1C—C2C—H2CC | 109.5 |
O1B—C9—H9 | 107.1 | H2CA—C2C—H2CC | 109.5 |
C10—C9—H9 | 107.1 | H2CB—C2C—H2CC | 109.5 |
C8—C9—H9 | 107.1 | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O2Ci | 0.85 (1) | 2.39 (3) | 3.120 (4) | 144 (4) |
O3—H3···O2Cii | 0.85 (1) | 1.99 (2) | 2.826 (4) | 168 (5) |
O1A—H1A···O2 | 0.85 (1) | 2.02 (3) | 2.769 (4) | 146 (5) |
C12—H12C···O1A | 0.96 | 2.29 | 3.020 (6) | 133 |
C13—H13A···O1B | 0.96 | 2.21 | 3.047 (4) | 146 |
C14—H14A···O1A | 0.96 | 2.52 | 3.147 (6) | 123 |
C4B—H4B···O2Biii | 0.93 | 2.56 | 3.421 (4) | 154 |
Symmetry codes: (i) x−1/2, −y+1/2, −z; (ii) −x+1/2, −y+1, z+1/2; (iii) x−1/2, −y+3/2, −z. |
The 16 [15?] reported structures with the same dihydro-β-agarofuran
skeleton
as
in (I). topNumber | CSD refcodea | Reference | Chemical name |
1 | ALEWOF | Mbaning et al. (2016) | 5-Acetoxy-2-hydroxy-2,6,10,10-tetramethyl-4-oxo-11-oxatricyclo[7.2.1.01,6]dodecane-7,12-diyl dibenzoate |
2 | ALEXOG | Mbaning et al. (2016) | 4,5,8-Triacetoxy-2-hydroxy-2,6,10,10-tetramethyl-11-oxatricyclo[7.2.1.01,6]dodecane-7,12-diyl dibenzoate hexane solvate |
3 | ALEYOH | Mbaning et al. (2016) | 4-Acetoxy-5,12-bis(benzoyloxy)-2-hydroxy-2,6,10,10-tetramethyl-11-oxatricyclo[7.2.1.01,6]dodec-7-yl nicotinate |
4 | CELBRB | Smith et al. (1976) | Celorbicol mono-p-bromobenzoate |
5 | EJACOI | Yeboah et al. (2010) | 2,6,10,10-Tetramethyl-4-oxo-11-oxatricyclo[7.2.1.01,6]dodecane-5,7-diyl bis(furan-3-carboxylate) |
6 | EJACOI01 | Yeboah et al. (2010) | 2,6,10,10-Tetramethyl-4-oxo-11-oxatricyclo[7.2.1.01,6]dodecane-5,7-diyl bis(furan-3-carboxylate) |
7 | ISOCEL | Smith et al. (1976) | Isocelorbicol |
8 | JAGREO | Hori et al. (1987) | Regelidine |
9 | KUXGEP | Yongqiang et al. (1990) | 1b,2b-Diacetoxy-9a-(3-phenyl-2-oxiranylcarboxy)-β-dihydroagarofuran |
10 | KUXGEP10 | Wang & Tu (1995) | 1b,2b-Diacetoxy-9a-(3-phenyl-2-oxiranylcarboxy)-β-dihydroagarofuran |
11 | OSOVUO | Torres-Romero et al. (2011) | 2,6,10,10-Tetramethyl-11-oxatricyclo[7.2.1.01,6]dodecane-2,5,7,8,12-pentol
hemihydrate |
12 | SIFNEA | Begley et al. (1990) | 6-O-Acetyl-9-O-[(E)-cinnamoyl]-1-O-glycoloyl-1,4,6,9-tetrahydroxydihydroagarofuran |
13 | UKUBIL | Mehta & Kumaran (2003) | 7-Benzoyloxy-2,6,10,10-tetramethyl-11-oxatricyclo[7.2.1.01,6]dodecane-3,4,12-triol |
14 | UKUBIL01 | Kumaran & Mehta (2015) | 7-Benzoyloxy-2,6,10,10-tetramethyl-11-oxatricyclo[7.2.1.01,6]dodecane-3,4,12-triol |
15 | YABZAC | Gonzalez et al. (1992) | (3S,4R,5R,7R,10R)-3,4-Dihydroxydihydro-β-agarofuran |
Reference: Groom et al. (2016). |
Hydrogen-bond geometry (Å, °) for (I) topCode | D—H···A | D—H | H···A | D···A | D—H···A | |
#1 | O1A—H1A···O2 | 0.851 (14) | 2.02 (3) | 2.769 (4) | 146 (5) | |
#2 | C12—H12C···O1A | 0.96 | 2.29 | 3.020 (6) | 133 | |
#3 | C14—H14A···O1A | 0.96 | 2.52 | 3.147 (6) | 123 | |
#4 | C13—H13A···O1B | 0.96 | 2.21 | 3.047 (4) | 146 | |
#5 | O3—H3···O2Ci | 0.848 (14) | 1.992 (18) | 2.826 (4) | 168 (5) | |
#6 | O2—H2···O2Cii | 0.854 (14) | 2.39 (3) | 3.120 (4) | 144 (4) | |
Symmetry codes: (i) -x+1/2, -y+1, z+1/2;
(ii) x-1/2, -y+1/2, -z. |
1H (600 MHz) and 13C (150 MHz) NMR data of MB 22 in DMSO-d6.
Chemical shifts (δ) in ppm and coupling constants (J) in Hz.
COSY is correlation spectroscopy and HMBC is heteronuclear multiple-bond
correlation spectroscopy. topPosition | 1H | 13C | COSY | HMBC |
1 | 5.07 (dd, J = 8.2, 5.2) | 72.5 | 2 a,b | 9, 10, 15, 1C |
2 | 1.68 (m) 1.45 (overlap) | 22.9 | 3 a,b | |
3 | 1.37 (m) 1.80 (td, J = 16.2, 4.5) | 35.4 | 2 a,b | 4, 7 |
4 | | 82.1 | | |
5 | | 91.4 | | |
6 | 4.78 (s) | 73.7 | 7 | 4, 8 |
7 | 2.10 (d, J = 3.8) | 57.4 | 6, 8 | 4, 5, 8, 9, 13 |
8 | 3.98 (t, J = 4.3) | 72.9 | 7 | 7, 9, 10 |
9 | 4.77 (d, J = 7.6) | 79.1 | | 5, 7, 8, 15, 1B |
10 | | 49.5 | | |
11 | | 71.8 | | |
12 | 1.46 (overlap) | 26.1 | | |
13 | 1.46 (overlap) | 30.2 | | |
14 | 1.38 (s) | 25.7 | | |
15 | 1.32 (s) | 19.8 | | 1, 5, 9, 10 |
1B | | 161.1 | | |
2B | | 118.5 | | |
3B | 8.16 (dd, J = 1.8, 0.9) | 148.4 | 4B | |
4B | 7.78 (t, J = 2.2) | 144.8 | 3B, 5B | |
5B | 6.66 (dd, J = 2.2, 0.9) | 109.4 | 4B | |
1C | | 169.4 | | 2C |
2C | 1.63 (s) | 20.7 | | 1C |