organic compounds
rac-(3aR,4S,5aR,6S,9R,10aS,10bR)-3a,5a,9-trimethyltetradecahydro-6,9-epoxycyclohepta[e]inden-4-ol monohydrate
ofaFakultät Chemie und Chemische Biologie, Technische Universität Dortmund, Otto-Hahn-Strasse 6, 44221 Dortmund, Germany
*Correspondence e-mail: hans.preut@tu-dortmund.de
The title hydrate, C17H28O2·H2O, was synthesized in order to determine the of the tetracyclic framework. The fused 5,6,7-tricarbocyclic core exhibits an entire cis-annulation, featuring a 1,4-cis-relation of the angular methyl groups in the six-membered ring. The oxa bridge of the epoxycycloheptane moiety is oriented towards the concave face of the boat-shaped molecule, whereas the angular methyl groups are directed towards the convex face. The of the crystal contains two nearly identical formula units, which are related via a pseudo-centre of symmetry. The structure could be solved in the space groups I-4 and I41/a. The in the acentric however, gave significantly better results and these are used in this paper. O—H⋯O hydrogen bonds are observed between the organic molecules, between the organic molecules and the water molecules, and between the water molecules, forming a chain along the c-axis direction.
Keywords: crystal structure; hydrate; hydrogen bonding; diterpenoid synthesis.
CCDC reference: 1419938
1. Related literature
For the total synthesis of jatrophane ); Schnabel et al. (2011). For the synthesis of norjatrophane see: Helmboldt et al. (2006); Helmboldt & Hiersemann (2009).
see: Schnabel & amp; Hiersemann (20092. Experimental
2.1. Crystal data
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2.2. Data collection
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2.3. Refinement
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Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell CrysAlis CCD; data reduction: CrysAlis CCD; program(s) used to solve structure: SHELXD (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
Supporting information
CCDC reference: 1419938
https://doi.org/10.1107/S2056989015015698/fk2090sup1.cif
contains datablocks I, 3000. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015015698/fk2090Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S2056989015015698/fk2090Isup3.cml
A sealable glass pressure tube was charged with freshly pestled sodium hydroxide (NaOH, M = 39.997 g/mol, 107 mg, 2.682 mmol, 50 eq) in dry methanol (6.8 ml, 125 ml/mmol). The suspension was stirred at room temperature until a clear colorless solution appeared (10 min). Then a solution of rac-(3aR,4S,5aR,6S,9R,\10aS,10bR)-3a,5a,9-trimethylτetradecahydro-6,9-epoxycyclohepta[e]inden-4-yl 4-bromobenzoate (II) (C24H31BrO3, M = 447.41 g/mol, 24.0 mg, 53.6 µmol, 1 eq) in methanol (6.8 ml, 125 ml/mmol) was added at 273 K. The cooling bath was removed and stirring was continued for 2 h at room temperature. Next, the tube was sealed with a Teflon screw cap and placed in a pre-heated oil bath (333 K). After being stirred for 17 h at 333 K, the reaction mixture was cooled to ambient temperature and diluted with saturated aqueous NH4Cl solution, water and dichloromethane. The resulting mixture was vigorously stirred for 15 min at room temperature. The phases were separated and the aqueous layer was extracted with CH2Cl2 (3x). The combined organic phases were dried (MgSO4) and the product was loaded directly onto silica gel. After removal of the volatiles under reduced pressure, purification by flash (cyclohexane/ethyl acetate 10/1 to 1/1) delivered rac-(3aR,4S,5aR,6S,\9R,10aS,10bR)-3a,5a,9-trimethyltetradecahydro-\6,9-epoxycyclohepta[e]inden-4-ol (I) (C17H28O2, M = 264.41 g/mol, 11.0 mg, 41.6 µmol, 78%) as a white solid. Crystallization of (I) from diethyl ether (5 ml, 120 ml/mmol) by slow evaporation under air provided colourless plates of the title hydrate. Rf 0.29 (cyclohexane/ethyl acetate 2/1); m.p. (monohydrate) 390–392 K; 1H NMR (CDCl3, 500 MHz) δ 0.83 (s, 3H), 1.07 (s, 3H), 1.22 (ddd, J = 13.0 Hz, J = 5.3 Hz, J = 1.1 Hz, 1H), 1.30–1.34 (m, 2H), 1.31 (s, 3H), 1.42–1.76 (m, 9H), 1.80–1.90 (m, 2H), 1.92–1.99 (m, 2H), 2.13 (dd, J = 13.0 Hz, J = 12.4 Hz, 1H), 3.64 (dd, J = 6.4 Hz, J = 1.6 Hz, 1H), 3.85 (dd, J = 12.4 Hz, J = 5.3 Hz, 1H); 13C NMR (CDCl3, 126 MHz) δ 20.9 (CH3), 21.1 (CH2), 26.1 (CH2), 26.9 (CH2), 27.0 (CH3), 28.2 (CH3), 31.6 (CH2), 34.2 (CH2), 35.0 (CH2), 36.9 (CH2), 37.3 (CH), 38.9 (C), 45.7 (CH), 48.2 (C), 74.9 (CH), 80.4 (C), 84.5 (CH); IR ν 3435 (s), 2955 (s), 2925 (s), 2870 (s), 1470 (s), 1450 (s), 1375 (s), 1235 (m), 1165 (m), 1085 (s), 1030 (s), 1010 (s), 810 (m), 730 (m); HRMS (ESI) Calcd. for C17H29O2 ([M+H]+): 265.21621; Found: 265.21672; Anal. Calcd. for C17H30O3 (monohydrate): C, 72.3; H, 10.7; Found: C, 72.1; H, 10.4.
H-atoms attached to C, except those of CH3, were placed at calculated positions (C—H = 0.99 - 1.00 Å and Uiso(H) = 1.2 Ueq(C)), while those attached to O were taken from a difference map and isotropically refined with constraints (DFIX 0.84 0.01 H O). All CH3 hydrogen atoms, which were taken from a Fourier map (AFIX 137), were allowed to rotate but not to tip (C—H = 0.98 Å and Uiso(H) = 1.5 Ueq(C)). The structure could be solved in the space groups I-4 and I41/a. The
in the acentric gave significantly better results and these are used in this paper. in I41/a was unstable, gave ADPs with several cigar-shaped ellipsoids and worse values for R1, wR2 and S. As in the absence of significant effects the is essentially meaningless, Friedel pairs were merged.As part of our studies in the total synthesis of
we afforded the 5,6,6,5-tetracyclic compound rac-(3aR,4S,5aR,6S,9R,10aS,10bR)-3a,5a,9-trimethyltetradecahydro-6,9-epoxycyclohepta[e]inden-4-yl 4-bromobenzoate (II). The saponification of (II) with sodium hydroxide in methanol provided rac-(3aR,4S,5aR,6S,9R,10aS,10bR)-3a,5a,9-trimethyltetradecahydro-6,9-epoxycyclohepta[e]inden-4-ol (I) as a white solid. Subsequent crystallization of (I) under air delivered the title hydrate.For the total synthesis of jatrophane
see: Schnabel et al. (2009, 2011). For the synthesis of norjatrophane see: Helmboldt et al. (2006, 2009).Data collection: CrysAlis CCD (Oxford Diffraction, 2008); cell
CrysAlis CCD (Oxford Diffraction, 2008); data reduction: CrysAlis CCD (Oxford Diffraction, 2008); program(s) used to solve structure: SHELXD (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2015); molecular graphics: SHELXTL-Plus (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).Fig. 1. : The molecular structure of the title compound with anisotropic displacement ellipsoids drawn at the 50% probability level. | |
Fig. 2. : Unit cell showing the 1-D network of molecules linked by intermolecular O—H ···O hydrogen bonds along crystallographic c axis. Hydrogen bonds between the C17H28O2 molecules, between C17H28O2 and water molecules and between water molecules are shown as dotted lines. H atoms not involved are omitted. |
C17H28O2·H2O | Dx = 1.209 Mg m−3 |
Mr = 282.41 | Mo Kα radiation, λ = 0.71073 Å |
Tetragonal, I4 | Cell parameters from 5041 reflections |
a = 25.3756 (9) Å | θ = 2.5–25.8° |
c = 9.6397 (6) Å | µ = 0.08 mm−1 |
V = 6207.2 (6) Å3 | T = 173 K |
Z = 16 | Plank, colourless |
F(000) = 2496 | 0.32 × 0.13 × 0.10 mm |
Agilent Xcalibur Sapphire3 diffractometer | 6781 independent reflections |
Radiation source: Enhance (Mo) X-ray Source | 4846 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.087 |
Detector resolution: 16.0560 pixels mm-1 | θmax = 27.0°, θmin = 2.3° |
ω scans | h = −31→31 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | k = −32→32 |
Tmin = 0.978, Tmax = 1.0 | l = −12→12 |
36469 measured reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.051 | Hydrogen site location: mixed |
wR(F2) = 0.109 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | w = 1/[σ2(Fo2) + (0.0458P)2] where P = (Fo2 + 2Fc2)/3 |
6781 reflections | (Δ/σ)max < 0.001 |
391 parameters | Δρmax = 0.19 e Å−3 |
6 restraints | Δρmin = −0.27 e Å−3 |
C17H28O2·H2O | Z = 16 |
Mr = 282.41 | Mo Kα radiation |
Tetragonal, I4 | µ = 0.08 mm−1 |
a = 25.3756 (9) Å | T = 173 K |
c = 9.6397 (6) Å | 0.32 × 0.13 × 0.10 mm |
V = 6207.2 (6) Å3 |
Agilent Xcalibur Sapphire3 diffractometer | 6781 independent reflections |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2014) | 4846 reflections with I > 2σ(I) |
Tmin = 0.978, Tmax = 1.0 | Rint = 0.087 |
36469 measured reflections |
R[F2 > 2σ(F2)] = 0.051 | 6 restraints |
wR(F2) = 0.109 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.03 | Δρmax = 0.19 e Å−3 |
6781 reflections | Δρmin = −0.27 e Å−3 |
391 parameters |
Experimental. Absorption correction: CrysAlis PRO, Agilent Technologies, Version 1.171.37.34 (release 22–05-2014 CrysAlis171. NET) (compiled May 22 2014,16:03:01) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.66099 (9) | 0.59249 (8) | 0.4355 (3) | 0.0213 (6) | |
O2 | 0.73096 (9) | 0.51802 (10) | 0.0043 (3) | 0.0258 (6) | |
H2 | 0.7353 (16) | 0.5049 (14) | −0.076 (2) | 0.050 (13)* | |
O6 | 0.75052 (11) | 0.46581 (11) | 0.7572 (3) | 0.0304 (6) | |
H6A | 0.7767 (9) | 0.4458 (11) | 0.768 (4) | 0.024 (10)* | |
H6B | 0.7522 (18) | 0.4812 (16) | 0.679 (3) | 0.061 (16)* | |
C1 | 0.67949 (15) | 0.68384 (14) | 0.4781 (4) | 0.0300 (9) | |
H1A | 0.7150 | 0.6801 | 0.4391 | 0.045* | |
H1B | 0.6804 | 0.6761 | 0.5777 | 0.045* | |
H1C | 0.6670 | 0.7200 | 0.4637 | 0.045* | |
C2 | 0.64250 (13) | 0.64565 (13) | 0.4066 (4) | 0.0216 (8) | |
C3 | 0.58635 (13) | 0.64494 (13) | 0.4660 (4) | 0.0263 (8) | |
H3A | 0.5625 | 0.6675 | 0.4105 | 0.032* | |
H3B | 0.5860 | 0.6572 | 0.5635 | 0.032* | |
C4 | 0.56997 (13) | 0.58639 (13) | 0.4558 (4) | 0.0268 (8) | |
H4A | 0.5624 | 0.5716 | 0.5488 | 0.032* | |
H4B | 0.5384 | 0.5821 | 0.3964 | 0.032* | |
C5 | 0.61801 (13) | 0.55991 (13) | 0.3907 (4) | 0.0213 (8) | |
H5 | 0.6222 | 0.5237 | 0.4299 | 0.026* | |
C6 | 0.61716 (12) | 0.55698 (12) | 0.2318 (4) | 0.0177 (7) | |
C7 | 0.57268 (13) | 0.51931 (13) | 0.1867 (4) | 0.0280 (9) | |
H7A | 0.5720 | 0.5170 | 0.0853 | 0.042* | |
H7B | 0.5388 | 0.5328 | 0.2202 | 0.042* | |
H7C | 0.5790 | 0.4843 | 0.2260 | 0.042* | |
C8 | 0.60877 (12) | 0.61283 (12) | 0.1714 (4) | 0.0183 (8) | |
H8 | 0.5714 | 0.6225 | 0.1923 | 0.022* | |
C9 | 0.64334 (12) | 0.65322 (13) | 0.2491 (4) | 0.0191 (8) | |
H9A | 0.6801 | 0.6501 | 0.2157 | 0.023* | |
H9B | 0.6308 | 0.6892 | 0.2269 | 0.023* | |
C10 | 0.61376 (12) | 0.61247 (12) | 0.0109 (4) | 0.0173 (8) | |
H10 | 0.5813 | 0.5957 | −0.0278 | 0.021* | |
C11 | 0.61827 (13) | 0.66842 (13) | −0.0518 (4) | 0.0232 (8) | |
H11A | 0.6002 | 0.6702 | −0.1427 | 0.028* | |
H11B | 0.6023 | 0.6948 | 0.0110 | 0.028* | |
C12 | 0.67794 (14) | 0.67872 (13) | −0.0688 (4) | 0.0263 (9) | |
H12A | 0.6855 | 0.6929 | −0.1624 | 0.032* | |
H12B | 0.6902 | 0.7046 | 0.0011 | 0.032* | |
C13 | 0.70590 (13) | 0.62545 (12) | −0.0479 (4) | 0.0232 (8) | |
H13A | 0.7247 | 0.6248 | 0.0420 | 0.028* | |
H13B | 0.7317 | 0.6191 | −0.1232 | 0.028* | |
C14 | 0.66210 (13) | 0.58337 (13) | −0.0508 (4) | 0.0191 (8) | |
C15 | 0.67692 (12) | 0.53245 (13) | 0.0275 (4) | 0.0190 (8) | |
H15 | 0.6540 | 0.5032 | −0.0071 | 0.023* | |
C16 | 0.67084 (13) | 0.53596 (13) | 0.1838 (4) | 0.0193 (8) | |
H16A | 0.6988 | 0.5592 | 0.2208 | 0.023* | |
H16B | 0.6762 | 0.5005 | 0.2239 | 0.023* | |
C17 | 0.65058 (14) | 0.56877 (15) | −0.2027 (4) | 0.0284 (9) | |
H17A | 0.6438 | 0.6009 | −0.2562 | 0.043* | |
H17B | 0.6196 | 0.5458 | −0.2067 | 0.043* | |
H17C | 0.6810 | 0.5503 | −0.2420 | 0.043* | |
O3 | 0.84108 (9) | 0.40046 (9) | −0.1931 (3) | 0.0228 (6) | |
O4 | 0.78753 (10) | 0.48936 (10) | 0.2508 (3) | 0.0308 (6) | |
H4 | 0.7724 (16) | 0.4988 (17) | 0.178 (3) | 0.062 (16)* | |
O5 | 0.74801 (11) | 0.52401 (11) | 0.5073 (3) | 0.0349 (7) | |
H5A | 0.7219 (12) | 0.5445 (15) | 0.499 (6) | 0.084 (19)* | |
H5B | 0.7591 (19) | 0.5138 (19) | 0.429 (3) | 0.088 (19)* | |
C18 | 0.80880 (15) | 0.31274 (14) | −0.2298 (5) | 0.0339 (10) | |
H18A | 0.8093 | 0.3188 | −0.3302 | 0.051* | |
H18B | 0.7745 | 0.3232 | −0.1923 | 0.051* | |
H18C | 0.8149 | 0.2753 | −0.2108 | 0.051* | |
C19 | 0.85175 (13) | 0.34518 (13) | −0.1618 (4) | 0.0224 (8) | |
C20 | 0.90685 (14) | 0.33742 (14) | −0.2224 (4) | 0.0301 (9) | |
H20A | 0.9049 | 0.3251 | −0.3197 | 0.036* | |
H20B | 0.9271 | 0.3115 | −0.1674 | 0.036* | |
C21 | 0.93216 (14) | 0.39215 (14) | −0.2139 (4) | 0.0298 (9) | |
H21A | 0.9423 | 0.4050 | −0.3072 | 0.036* | |
H21B | 0.9638 | 0.3916 | −0.1537 | 0.036* | |
C22 | 0.88853 (13) | 0.42672 (14) | −0.1508 (4) | 0.0244 (8) | |
H22 | 0.8899 | 0.4628 | −0.1924 | 0.029* | |
C23 | 0.89047 (13) | 0.43070 (13) | 0.0088 (4) | 0.0209 (8) | |
C24 | 0.93975 (13) | 0.46248 (14) | 0.0502 (4) | 0.0314 (9) | |
H24A | 0.9382 | 0.4975 | 0.0075 | 0.047* | |
H24B | 0.9714 | 0.4440 | 0.0182 | 0.047* | |
H24C | 0.9410 | 0.4662 | 0.1514 | 0.047* | |
C25 | 0.89094 (12) | 0.37507 (13) | 0.0714 (4) | 0.0195 (8) | |
H25 | 0.9265 | 0.3601 | 0.0502 | 0.023* | |
C26 | 0.85069 (13) | 0.33920 (13) | −0.0037 (4) | 0.0215 (8) | |
H26A | 0.8582 | 0.3020 | 0.0204 | 0.026* | |
H26B | 0.8149 | 0.3476 | 0.0303 | 0.026* | |
C27 | 0.88639 (12) | 0.37606 (12) | 0.2315 (4) | 0.0194 (8) | |
H27 | 0.9210 | 0.3880 | 0.2699 | 0.023* | |
C28 | 0.87333 (13) | 0.32212 (13) | 0.2959 (4) | 0.0251 (8) | |
H28A | 0.8855 | 0.2933 | 0.2347 | 0.030* | |
H28B | 0.8906 | 0.3183 | 0.3874 | 0.030* | |
C29 | 0.81308 (14) | 0.32045 (13) | 0.3117 (4) | 0.0272 (9) | |
H29A | 0.8033 | 0.3077 | 0.4053 | 0.033* | |
H29B | 0.7974 | 0.2965 | 0.2418 | 0.033* | |
C30 | 0.79305 (13) | 0.37761 (13) | 0.2896 (4) | 0.0237 (8) | |
H30A | 0.7747 | 0.3809 | 0.1994 | 0.028* | |
H30B | 0.7684 | 0.3878 | 0.3645 | 0.028* | |
C31 | 0.84251 (12) | 0.41241 (13) | 0.2926 (4) | 0.0200 (8) | |
C32 | 0.83662 (13) | 0.46477 (13) | 0.2139 (4) | 0.0236 (8) | |
H32 | 0.8657 | 0.4886 | 0.2451 | 0.028* | |
C33 | 0.84067 (13) | 0.45958 (13) | 0.0579 (4) | 0.0207 (8) | |
H33A | 0.8402 | 0.4953 | 0.0163 | 0.025* | |
H33B | 0.8093 | 0.4404 | 0.0234 | 0.025* | |
C34 | 0.85574 (14) | 0.42541 (14) | 0.4452 (4) | 0.0296 (9) | |
H34A | 0.8560 | 0.3929 | 0.4999 | 0.044* | |
H34B | 0.8291 | 0.4495 | 0.4825 | 0.044* | |
H34C | 0.8905 | 0.4421 | 0.4500 | 0.044* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0250 (13) | 0.0208 (12) | 0.0182 (14) | 0.0045 (10) | −0.0002 (10) | 0.0000 (10) |
O2 | 0.0251 (14) | 0.0325 (15) | 0.0199 (15) | 0.0134 (11) | 0.0007 (11) | −0.0012 (12) |
O6 | 0.0295 (15) | 0.0372 (16) | 0.0245 (16) | 0.0122 (13) | 0.0004 (13) | −0.0016 (13) |
C1 | 0.039 (2) | 0.032 (2) | 0.019 (2) | 0.0025 (17) | −0.0010 (17) | −0.0052 (17) |
C2 | 0.0256 (19) | 0.0194 (18) | 0.020 (2) | 0.0064 (15) | 0.0000 (15) | −0.0027 (15) |
C3 | 0.029 (2) | 0.030 (2) | 0.020 (2) | 0.0094 (15) | 0.0055 (16) | −0.0004 (17) |
C4 | 0.0252 (19) | 0.032 (2) | 0.023 (2) | 0.0007 (16) | 0.0059 (16) | 0.0034 (16) |
C5 | 0.0217 (19) | 0.0206 (19) | 0.022 (2) | −0.0002 (15) | 0.0013 (15) | 0.0039 (15) |
C6 | 0.0172 (17) | 0.0171 (17) | 0.0188 (19) | −0.0006 (13) | 0.0027 (15) | 0.0025 (14) |
C7 | 0.030 (2) | 0.026 (2) | 0.028 (2) | −0.0068 (16) | 0.0019 (17) | 0.0016 (17) |
C8 | 0.0112 (16) | 0.0232 (18) | 0.020 (2) | 0.0025 (14) | 0.0017 (14) | −0.0004 (15) |
C9 | 0.0183 (17) | 0.0175 (17) | 0.022 (2) | 0.0013 (14) | 0.0008 (15) | 0.0008 (15) |
C10 | 0.0163 (17) | 0.0214 (18) | 0.0143 (19) | 0.0006 (14) | −0.0020 (14) | 0.0009 (14) |
C11 | 0.0257 (19) | 0.0263 (19) | 0.018 (2) | 0.0058 (15) | 0.0009 (16) | 0.0027 (15) |
C12 | 0.031 (2) | 0.0223 (19) | 0.025 (2) | −0.0002 (15) | 0.0020 (17) | 0.0053 (16) |
C13 | 0.0222 (19) | 0.0278 (19) | 0.020 (2) | 0.0021 (15) | 0.0042 (16) | 0.0047 (17) |
C14 | 0.0192 (18) | 0.0222 (18) | 0.0159 (19) | 0.0056 (14) | 0.0004 (15) | −0.0004 (15) |
C15 | 0.0176 (17) | 0.0201 (18) | 0.0192 (19) | 0.0042 (13) | 0.0004 (14) | −0.0012 (15) |
C16 | 0.0198 (18) | 0.0198 (18) | 0.0183 (19) | 0.0017 (14) | −0.0012 (14) | 0.0022 (15) |
C17 | 0.030 (2) | 0.036 (2) | 0.020 (2) | 0.0096 (16) | −0.0001 (17) | −0.0002 (17) |
O3 | 0.0232 (13) | 0.0230 (13) | 0.0224 (14) | 0.0051 (10) | −0.0009 (11) | 0.0018 (11) |
O4 | 0.0348 (15) | 0.0374 (15) | 0.0201 (15) | 0.0189 (12) | −0.0001 (12) | −0.0016 (12) |
O5 | 0.0362 (17) | 0.0435 (17) | 0.0249 (17) | 0.0149 (14) | −0.0010 (14) | −0.0008 (14) |
C18 | 0.039 (2) | 0.032 (2) | 0.031 (2) | 0.0047 (18) | 0.0008 (19) | −0.0083 (18) |
C19 | 0.025 (2) | 0.0228 (19) | 0.019 (2) | 0.0065 (15) | 0.0024 (15) | 0.0023 (16) |
C20 | 0.032 (2) | 0.035 (2) | 0.023 (2) | 0.0110 (17) | 0.0044 (17) | 0.0010 (18) |
C21 | 0.025 (2) | 0.045 (2) | 0.020 (2) | 0.0035 (17) | 0.0083 (15) | 0.0069 (18) |
C22 | 0.0221 (19) | 0.026 (2) | 0.025 (2) | 0.0011 (16) | 0.0050 (16) | 0.0076 (16) |
C23 | 0.0186 (18) | 0.0193 (18) | 0.025 (2) | −0.0003 (14) | 0.0019 (15) | 0.0054 (15) |
C24 | 0.0239 (19) | 0.032 (2) | 0.038 (2) | −0.0071 (16) | 0.0020 (18) | 0.0081 (18) |
C25 | 0.0149 (17) | 0.0240 (19) | 0.020 (2) | 0.0041 (14) | 0.0020 (15) | 0.0051 (15) |
C26 | 0.0237 (19) | 0.0178 (18) | 0.023 (2) | 0.0006 (14) | 0.0012 (16) | 0.0012 (15) |
C27 | 0.0157 (17) | 0.0188 (18) | 0.024 (2) | 0.0023 (13) | −0.0029 (15) | 0.0025 (15) |
C28 | 0.029 (2) | 0.0245 (19) | 0.022 (2) | 0.0068 (15) | 0.0002 (17) | 0.0048 (16) |
C29 | 0.031 (2) | 0.026 (2) | 0.025 (2) | −0.0026 (16) | 0.0046 (17) | 0.0038 (17) |
C30 | 0.0201 (18) | 0.029 (2) | 0.022 (2) | 0.0010 (15) | 0.0041 (16) | 0.0026 (17) |
C31 | 0.0197 (18) | 0.0238 (19) | 0.0167 (19) | 0.0011 (14) | −0.0018 (15) | 0.0003 (15) |
C32 | 0.0193 (18) | 0.0239 (19) | 0.028 (2) | 0.0027 (14) | −0.0030 (16) | −0.0018 (16) |
C33 | 0.0236 (18) | 0.0175 (17) | 0.021 (2) | 0.0032 (14) | −0.0020 (16) | 0.0051 (15) |
C34 | 0.033 (2) | 0.031 (2) | 0.025 (2) | 0.0045 (17) | −0.0052 (18) | −0.0001 (18) |
O1—C5 | 1.435 (4) | O3—C22 | 1.435 (4) |
O1—C2 | 1.455 (4) | O3—C19 | 1.460 (4) |
O2—C15 | 1.437 (4) | O4—C32 | 1.438 (4) |
O2—H2 | 0.846 (14) | O4—H4 | 0.838 (14) |
O6—H6A | 0.844 (13) | O5—H5A | 0.845 (14) |
O6—H6B | 0.847 (14) | O5—H5B | 0.848 (14) |
C1—C2 | 1.515 (5) | C18—C19 | 1.515 (5) |
C1—H1A | 0.9800 | C18—H18A | 0.9800 |
C1—H1B | 0.9800 | C18—H18B | 0.9800 |
C1—H1C | 0.9800 | C18—H18C | 0.9800 |
C2—C9 | 1.530 (5) | C19—C20 | 1.528 (5) |
C2—C3 | 1.536 (5) | C19—C26 | 1.532 (5) |
C3—C4 | 1.546 (5) | C20—C21 | 1.532 (5) |
C3—H3A | 0.9900 | C20—H20A | 0.9900 |
C3—H3B | 0.9900 | C20—H20B | 0.9900 |
C4—C5 | 1.527 (5) | C21—C22 | 1.538 (5) |
C4—H4A | 0.9900 | C21—H21A | 0.9900 |
C4—H4B | 0.9900 | C21—H21B | 0.9900 |
C5—C6 | 1.533 (5) | C22—C23 | 1.542 (5) |
C5—H5 | 1.0000 | C22—H22 | 1.0000 |
C6—C16 | 1.535 (4) | C23—C25 | 1.535 (4) |
C6—C7 | 1.542 (4) | C23—C33 | 1.536 (5) |
C6—C8 | 1.547 (4) | C23—C24 | 1.541 (5) |
C7—H7A | 0.9800 | C24—H24A | 0.9800 |
C7—H7B | 0.9800 | C24—H24B | 0.9800 |
C7—H7C | 0.9800 | C24—H24C | 0.9800 |
C8—C9 | 1.543 (5) | C25—C26 | 1.548 (5) |
C8—C10 | 1.553 (5) | C25—C27 | 1.548 (5) |
C8—H8 | 1.0000 | C25—H25 | 1.0000 |
C9—H9A | 0.9900 | C26—H26A | 0.9900 |
C9—H9B | 0.9900 | C26—H26B | 0.9900 |
C10—C11 | 1.547 (4) | C27—C28 | 1.539 (4) |
C10—C14 | 1.550 (4) | C27—C31 | 1.561 (5) |
C10—H10 | 1.0000 | C27—H27 | 1.0000 |
C11—C12 | 1.545 (5) | C28—C29 | 1.537 (5) |
C11—H11A | 0.9900 | C28—H28A | 0.9900 |
C11—H11B | 0.9900 | C28—H28B | 0.9900 |
C12—C13 | 1.540 (4) | C29—C30 | 1.551 (5) |
C12—H12A | 0.9900 | C29—H29A | 0.9900 |
C12—H12B | 0.9900 | C29—H29B | 0.9900 |
C13—C14 | 1.542 (4) | C30—C31 | 1.535 (4) |
C13—H13A | 0.9900 | C30—H30A | 0.9900 |
C13—H13B | 0.9900 | C30—H30B | 0.9900 |
C14—C17 | 1.539 (5) | C31—C32 | 1.537 (5) |
C14—C15 | 1.543 (4) | C31—C34 | 1.545 (5) |
C15—C16 | 1.517 (5) | C32—C33 | 1.513 (5) |
C15—H15 | 1.0000 | C32—H32 | 1.0000 |
C16—H16A | 0.9900 | C33—H33A | 0.9900 |
C16—H16B | 0.9900 | C33—H33B | 0.9900 |
C17—H17A | 0.9800 | C34—H34A | 0.9800 |
C17—H17B | 0.9800 | C34—H34B | 0.9800 |
C17—H17C | 0.9800 | C34—H34C | 0.9800 |
C5—O1—C2 | 103.4 (2) | C22—O3—C19 | 103.4 (2) |
C15—O2—H2 | 112 (3) | C32—O4—H4 | 108 (3) |
H6A—O6—H6B | 111 (4) | H5A—O5—H5B | 111 (5) |
C2—C1—H1A | 109.5 | C19—C18—H18A | 109.5 |
C2—C1—H1B | 109.5 | C19—C18—H18B | 109.5 |
H1A—C1—H1B | 109.5 | H18A—C18—H18B | 109.5 |
C2—C1—H1C | 109.5 | C19—C18—H18C | 109.5 |
H1A—C1—H1C | 109.5 | H18A—C18—H18C | 109.5 |
H1B—C1—H1C | 109.5 | H18B—C18—H18C | 109.5 |
O1—C2—C1 | 107.8 (3) | O3—C19—C18 | 107.4 (3) |
O1—C2—C9 | 107.6 (3) | O3—C19—C20 | 102.4 (3) |
C1—C2—C9 | 111.3 (3) | C18—C19—C20 | 115.0 (3) |
O1—C2—C3 | 102.5 (3) | O3—C19—C26 | 107.3 (3) |
C1—C2—C3 | 114.4 (3) | C18—C19—C26 | 111.3 (3) |
C9—C2—C3 | 112.6 (3) | C20—C19—C26 | 112.6 (3) |
C2—C3—C4 | 103.7 (3) | C19—C20—C21 | 104.3 (3) |
C2—C3—H3A | 111.0 | C19—C20—H20A | 110.9 |
C4—C3—H3A | 111.0 | C21—C20—H20A | 110.9 |
C2—C3—H3B | 111.0 | C19—C20—H20B | 110.9 |
C4—C3—H3B | 111.0 | C21—C20—H20B | 110.9 |
H3A—C3—H3B | 109.0 | H20A—C20—H20B | 108.9 |
C5—C4—C3 | 103.6 (3) | C20—C21—C22 | 103.7 (3) |
C5—C4—H4A | 111.0 | C20—C21—H21A | 111.0 |
C3—C4—H4A | 111.0 | C22—C21—H21A | 111.0 |
C5—C4—H4B | 111.0 | C20—C21—H21B | 111.0 |
C3—C4—H4B | 111.0 | C22—C21—H21B | 111.0 |
H4A—C4—H4B | 109.0 | H21A—C21—H21B | 109.0 |
O1—C5—C4 | 103.3 (3) | O3—C22—C21 | 103.1 (3) |
O1—C5—C6 | 109.8 (3) | O3—C22—C23 | 109.9 (3) |
C4—C5—C6 | 114.9 (3) | C21—C22—C23 | 114.2 (3) |
O1—C5—H5 | 109.5 | O3—C22—H22 | 109.8 |
C4—C5—H5 | 109.5 | C21—C22—H22 | 109.8 |
C6—C5—H5 | 109.5 | C23—C22—H22 | 109.8 |
C5—C6—C16 | 107.8 (3) | C25—C23—C33 | 108.9 (3) |
C5—C6—C7 | 108.8 (3) | C25—C23—C24 | 111.9 (3) |
C16—C6—C7 | 110.4 (3) | C33—C23—C24 | 109.8 (3) |
C5—C6—C8 | 109.5 (3) | C25—C23—C22 | 109.4 (3) |
C16—C6—C8 | 109.1 (3) | C33—C23—C22 | 108.2 (3) |
C7—C6—C8 | 111.2 (3) | C24—C23—C22 | 108.6 (3) |
C6—C7—H7A | 109.5 | C23—C24—H24A | 109.5 |
C6—C7—H7B | 109.5 | C23—C24—H24B | 109.5 |
H7A—C7—H7B | 109.5 | H24A—C24—H24B | 109.5 |
C6—C7—H7C | 109.5 | C23—C24—H24C | 109.5 |
H7A—C7—H7C | 109.5 | H24A—C24—H24C | 109.5 |
H7B—C7—H7C | 109.5 | H24B—C24—H24C | 109.5 |
C9—C8—C6 | 110.3 (3) | C23—C25—C26 | 110.6 (3) |
C9—C8—C10 | 116.2 (3) | C23—C25—C27 | 112.1 (3) |
C6—C8—C10 | 111.0 (3) | C26—C25—C27 | 115.2 (3) |
C9—C8—H8 | 106.2 | C23—C25—H25 | 106.1 |
C6—C8—H8 | 106.2 | C26—C25—H25 | 106.1 |
C10—C8—H8 | 106.2 | C27—C25—H25 | 106.1 |
C2—C9—C8 | 112.9 (3) | C19—C26—C25 | 113.3 (3) |
C2—C9—H9A | 109.0 | C19—C26—H26A | 108.9 |
C8—C9—H9A | 109.0 | C25—C26—H26A | 108.9 |
C2—C9—H9B | 109.0 | C19—C26—H26B | 108.9 |
C8—C9—H9B | 109.0 | C25—C26—H26B | 108.9 |
H9A—C9—H9B | 107.8 | H26A—C26—H26B | 107.7 |
C11—C10—C14 | 103.2 (3) | C28—C27—C25 | 113.8 (3) |
C11—C10—C8 | 112.9 (3) | C28—C27—C31 | 102.7 (3) |
C14—C10—C8 | 116.7 (3) | C25—C27—C31 | 116.0 (3) |
C11—C10—H10 | 107.9 | C28—C27—H27 | 108.0 |
C14—C10—H10 | 107.9 | C25—C27—H27 | 108.0 |
C8—C10—H10 | 107.9 | C31—C27—H27 | 108.0 |
C12—C11—C10 | 105.6 (3) | C29—C28—C27 | 106.2 (3) |
C12—C11—H11A | 110.6 | C29—C28—H28A | 110.5 |
C10—C11—H11A | 110.6 | C27—C28—H28A | 110.5 |
C12—C11—H11B | 110.6 | C29—C28—H28B | 110.5 |
C10—C11—H11B | 110.6 | C27—C28—H28B | 110.5 |
H11A—C11—H11B | 108.7 | H28A—C28—H28B | 108.7 |
C13—C12—C11 | 106.8 (3) | C28—C29—C30 | 106.6 (3) |
C13—C12—H12A | 110.4 | C28—C29—H29A | 110.4 |
C11—C12—H12A | 110.4 | C30—C29—H29A | 110.4 |
C13—C12—H12B | 110.4 | C28—C29—H29B | 110.4 |
C11—C12—H12B | 110.4 | C30—C29—H29B | 110.4 |
H12A—C12—H12B | 108.6 | H29A—C29—H29B | 108.6 |
C12—C13—C14 | 105.9 (3) | C31—C30—C29 | 105.5 (3) |
C12—C13—H13A | 110.6 | C31—C30—H30A | 110.6 |
C14—C13—H13A | 110.6 | C29—C30—H30A | 110.6 |
C12—C13—H13B | 110.6 | C31—C30—H30B | 110.6 |
C14—C13—H13B | 110.6 | C29—C30—H30B | 110.6 |
H13A—C13—H13B | 108.7 | H30A—C30—H30B | 108.8 |
C17—C14—C13 | 108.7 (3) | C30—C31—C32 | 114.1 (3) |
C17—C14—C15 | 108.1 (3) | C30—C31—C34 | 108.6 (3) |
C13—C14—C15 | 113.3 (3) | C32—C31—C34 | 107.8 (3) |
C17—C14—C10 | 109.2 (3) | C30—C31—C27 | 103.7 (3) |
C13—C14—C10 | 103.5 (3) | C32—C31—C27 | 113.2 (3) |
C15—C14—C10 | 113.9 (3) | C34—C31—C27 | 109.3 (3) |
O2—C15—C16 | 105.5 (3) | O4—C32—C33 | 110.1 (3) |
O2—C15—C14 | 111.7 (3) | O4—C32—C31 | 109.7 (3) |
C16—C15—C14 | 114.3 (3) | C33—C32—C31 | 114.1 (3) |
O2—C15—H15 | 108.4 | O4—C32—H32 | 107.6 |
C16—C15—H15 | 108.4 | C33—C32—H32 | 107.6 |
C14—C15—H15 | 108.4 | C31—C32—H32 | 107.6 |
C15—C16—C6 | 114.2 (3) | C32—C33—C23 | 113.8 (3) |
C15—C16—H16A | 108.7 | C32—C33—H33A | 108.8 |
C6—C16—H16A | 108.7 | C23—C33—H33A | 108.8 |
C15—C16—H16B | 108.7 | C32—C33—H33B | 108.8 |
C6—C16—H16B | 108.7 | C23—C33—H33B | 108.8 |
H16A—C16—H16B | 107.6 | H33A—C33—H33B | 107.7 |
C14—C17—H17A | 109.5 | C31—C34—H34A | 109.5 |
C14—C17—H17B | 109.5 | C31—C34—H34B | 109.5 |
H17A—C17—H17B | 109.5 | H34A—C34—H34B | 109.5 |
C14—C17—H17C | 109.5 | C31—C34—H34C | 109.5 |
H17A—C17—H17C | 109.5 | H34A—C34—H34C | 109.5 |
H17B—C17—H17C | 109.5 | H34B—C34—H34C | 109.5 |
C5—O1—C2—C1 | 167.9 (3) | C22—O3—C19—C18 | −168.4 (3) |
C5—O1—C2—C9 | −72.1 (3) | C22—O3—C19—C20 | −46.9 (3) |
C5—O1—C2—C3 | 46.8 (3) | C22—O3—C19—C26 | 71.8 (3) |
O1—C2—C3—C4 | −27.2 (3) | O3—C19—C20—C21 | 28.1 (4) |
C1—C2—C3—C4 | −143.6 (3) | C18—C19—C20—C21 | 144.3 (3) |
C9—C2—C3—C4 | 88.1 (3) | C26—C19—C20—C21 | −86.8 (3) |
C2—C3—C4—C5 | −0.5 (4) | C19—C20—C21—C22 | −0.8 (4) |
C2—O1—C5—C4 | −47.5 (3) | C19—O3—C22—C21 | 46.5 (3) |
C2—O1—C5—C6 | 75.5 (3) | C19—O3—C22—C23 | −75.6 (3) |
C3—C4—C5—O1 | 28.6 (3) | C20—C21—C22—O3 | −27.3 (4) |
C3—C4—C5—C6 | −91.0 (3) | C20—C21—C22—C23 | 91.9 (4) |
O1—C5—C6—C16 | 57.0 (3) | O3—C22—C23—C25 | 61.6 (3) |
C4—C5—C6—C16 | 172.9 (3) | C21—C22—C23—C25 | −53.6 (4) |
O1—C5—C6—C7 | 176.8 (2) | O3—C22—C23—C33 | −56.9 (4) |
C4—C5—C6—C7 | −67.3 (4) | C21—C22—C23—C33 | −172.2 (3) |
O1—C5—C6—C8 | −61.5 (3) | O3—C22—C23—C24 | −176.0 (2) |
C4—C5—C6—C8 | 54.3 (4) | C21—C22—C23—C24 | 68.7 (4) |
C5—C6—C8—C9 | 43.5 (4) | C33—C23—C25—C26 | 74.8 (3) |
C16—C6—C8—C9 | −74.2 (3) | C24—C23—C25—C26 | −163.7 (3) |
C7—C6—C8—C9 | 163.8 (3) | C22—C23—C25—C26 | −43.3 (4) |
C5—C6—C8—C10 | 173.8 (3) | C33—C23—C25—C27 | −55.3 (3) |
C16—C6—C8—C10 | 56.1 (3) | C24—C23—C25—C27 | 66.2 (4) |
C7—C6—C8—C10 | −66.0 (3) | C22—C23—C25—C27 | −173.4 (3) |
O1—C2—C9—C8 | 58.6 (3) | O3—C19—C26—C25 | −58.1 (4) |
C1—C2—C9—C8 | 176.5 (3) | C18—C19—C26—C25 | −175.4 (3) |
C3—C2—C9—C8 | −53.6 (4) | C20—C19—C26—C25 | 53.8 (4) |
C6—C8—C9—C2 | −43.9 (4) | C23—C25—C26—C19 | 43.8 (4) |
C10—C8—C9—C2 | −171.4 (3) | C27—C25—C26—C19 | 172.2 (3) |
C9—C8—C10—C11 | −39.9 (4) | C23—C25—C27—C28 | 166.1 (3) |
C6—C8—C10—C11 | −167.0 (2) | C26—C25—C27—C28 | 38.4 (4) |
C9—C8—C10—C14 | 79.5 (4) | C23—C25—C27—C31 | 47.2 (4) |
C6—C8—C10—C14 | −47.6 (4) | C26—C25—C27—C31 | −80.5 (4) |
C14—C10—C11—C12 | −31.8 (3) | C25—C27—C28—C29 | −93.9 (3) |
C8—C10—C11—C12 | 95.1 (3) | C31—C27—C28—C29 | 32.3 (4) |
C10—C11—C12—C13 | 12.5 (4) | C27—C28—C29—C30 | −13.2 (4) |
C11—C12—C13—C14 | 11.9 (4) | C28—C29—C30—C31 | −11.7 (4) |
C12—C13—C14—C17 | 84.5 (3) | C29—C30—C31—C32 | 155.2 (3) |
C12—C13—C14—C15 | −155.4 (3) | C29—C30—C31—C34 | −84.5 (3) |
C12—C13—C14—C10 | −31.6 (3) | C29—C30—C31—C27 | 31.6 (3) |
C11—C10—C14—C17 | −76.7 (3) | C28—C27—C31—C30 | −39.4 (3) |
C8—C10—C14—C17 | 158.8 (3) | C25—C27—C31—C30 | 85.4 (3) |
C11—C10—C14—C13 | 39.0 (3) | C28—C27—C31—C32 | −163.6 (3) |
C8—C10—C14—C13 | −85.5 (3) | C25—C27—C31—C32 | −38.8 (4) |
C11—C10—C14—C15 | 162.5 (3) | C28—C27—C31—C34 | 76.2 (3) |
C8—C10—C14—C15 | 38.0 (4) | C25—C27—C31—C34 | −159.0 (3) |
C17—C14—C15—O2 | 80.7 (3) | C30—C31—C32—O4 | 46.5 (4) |
C13—C14—C15—O2 | −39.8 (4) | C34—C31—C32—O4 | −74.2 (3) |
C10—C14—C15—O2 | −157.8 (3) | C27—C31—C32—O4 | 164.7 (3) |
C17—C14—C15—C16 | −159.7 (3) | C30—C31—C32—C33 | −77.5 (4) |
C13—C14—C15—C16 | 79.8 (4) | C34—C31—C32—C33 | 161.8 (3) |
C10—C14—C15—C16 | −38.2 (4) | C27—C31—C32—C33 | 40.7 (4) |
O2—C15—C16—C6 | 173.6 (2) | O4—C32—C33—C23 | −176.6 (3) |
C14—C15—C16—C6 | 50.5 (4) | C31—C32—C33—C23 | −52.7 (4) |
C5—C6—C16—C15 | −178.1 (3) | C25—C23—C33—C32 | 59.4 (4) |
C7—C6—C16—C15 | 63.2 (4) | C24—C23—C33—C32 | −63.5 (4) |
C8—C6—C16—C15 | −59.3 (4) | C22—C23—C33—C32 | 178.2 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O6i | 0.85 (1) | 1.93 (2) | 2.770 (4) | 171 (4) |
O6—H6A···O3ii | 0.84 (1) | 2.03 (1) | 2.874 (3) | 176 (4) |
O4—H4···O2 | 0.84 (1) | 2.03 (2) | 2.871 (3) | 176 (4) |
O5—H5A···O1 | 0.85 (1) | 2.06 (2) | 2.894 (3) | 169 (5) |
O6—H6B···O5 | 0.85 (1) | 1.99 (2) | 2.826 (4) | 172 (5) |
O5—H5B···O4 | 0.85 (1) | 1.96 (2) | 2.809 (4) | 178 (5) |
Symmetry codes: (i) x, y, z−1; (ii) x, y, z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H2···O6i | 0.846 (14) | 1.932 (16) | 2.770 (4) | 171 (4) |
O6—H6A···O3ii | 0.844 (13) | 2.032 (14) | 2.874 (3) | 176 (4) |
O4—H4···O2 | 0.838 (14) | 2.034 (15) | 2.871 (3) | 176 (4) |
O5—H5A···O1 | 0.845 (14) | 2.061 (18) | 2.894 (3) | 169 (5) |
O6—H6B···O5 | 0.847 (14) | 1.985 (16) | 2.826 (4) | 172 (5) |
O5—H5B···O4 | 0.848 (14) | 1.961 (15) | 2.809 (4) | 178 (5) |
Symmetry codes: (i) x, y, z−1; (ii) x, y, z+1. |
Acknowledgements
Financial support by the Fonds der Chemischen Industrie (FCI) and the TU Dortmund is gratefully acknowledged.
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As part of our studies in the total synthesis of diterpenoids, we afforded the 5,6,6,5-tetracyclic compound rac-(3aR,4S,5aR,6S,9R,10aS,10bR)-3a,5a,9-trimethyltetradecahydro-6,9-epoxycyclohepta[e]inden-4-yl 4-bromobenzoate (II). The saponification of (II) with sodium hydroxide in methanol provided rac-(3aR,4S,5aR,6S,9R,10aS,10bR)-3a,5a,9-trimethyltetradecahydro-6,9-epoxycyclohepta[e]inden-4-ol (I) as a white solid. Subsequent crystallization of (I) under air delivered the title hydrate.