organic compounds
(25R)-6α-Hydroxy-5α-spirostan-3β-yl tosylate
aBenemérita Universidad Autónoma de Puebla, Facultad de Ciencias Químicas, Ciudad Universitaria, Puebla, Pue. 72570, Mexico, bUniversidad Autónoma de Nuevo León, UANL, Facultad de Ciencias Químicas, Av. Universidad S/N, Ciudad Universitaria, San Nicolás de los Garza, Nuevo León CP 66451, Mexico, cHerbario y Jardín Botánico, Benemérita Universidad Autónoma de Puebla, Ciudad Universitaria, Puebla, Pue. 72570, Mexico, and dEscuelas de Ingeniería en Petróleos e Ingeniería Química, Universidad del Istmo, Ciudad Universitaria s/n, 70760 Sto. Domingo Tehuantepec, Oax., Mexico
*Correspondence e-mail: sylvain_bernes@hotmail.com
The title steroid, C34H50O6S, is an intermediate on the synthetic route between diosgenin and brassinosteroids, which possess the A ring modified with the 2α,3α-diol functionality. The polycyclic spirostan system has the expected conformation, with six-membered rings adopting chair forms and the five-membered rings envelope forms (flap atoms are the methine C atom in the C/D-ring junction and the spiro C atom connecting rings E and F). The 3β-tosylate group is oriented in such a way that S=O bonds are engaged in intermolecular hydrogen bonds with O—H and C—H donors. Chains of molecules are formed along [100] via O—H⋯O hydrogen bonds, and secondary weak C—H⋯O interactions connect two neighbouring chains in the [001] direction.
Related literature
For background to brassinosteroids, see: Asami et al. (2005); Kang & Guo (2011); Zullo & Adam (2002). For the hydroboration-oxidation synthetic step used for the preparation of the title compound, see: Smith & Pelter (1991); Brown (1962). For the structure of another steroid functionalized at C-3 with a tosylate group, see: Cox et al. (1996).
Experimental
Crystal data
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Data collection: XSCANS (Siemens, 1996); cell XSCANS; data reduction: XSCANS; 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: SHELXL97.
Supporting information
10.1107/S1600536812046600/bq2379sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812046600/bq2379Isup2.hkl
Diosgenin (750 mg, 1.8 mmol) was tosylated by means of p-TsCl/py/DCM, following the standard procedure, affording diosgenin tosylate quantitatively; the crude was properly washed, dried and immediately submitted to the next reaction. Diosgenin tosylate (1 g, 1.76 mmol) was dissolved in THF (30 ml) and NaBH4 (0.4 g, 10.8 mmol) was added. The system was sealed under Ar atmosphere and then, BF3.Et2O (0.7 ml, 5.6 mmol) was carefully added. The reaction mixture was kept for 2 h at room temperature, concentrated under reduced pressure, and re-dissolved in a solution of KOH/MeOH (2%, 50 ml), followed by 5 ml of 35% H2O2. The reaction mixture was stirred for 1 h; then the addition of water produced a precipitate, which was filtered off, washed with cold water, and dried under high vacuum. The resulting white powder was purified by α]D -39° (c 1.0, CHCl3). Spectroscopic characterization may be found in the archived CIF.
with hexanes/EtOAc 7:3 to afford the title compound as a white powder. It was recrystallized from hexanes/EtOAc 8:2 to obtain 0.72 g (70%) of colourless crystals. M.p. 149–150 °C, [Hydroxyl H atom H30 was found in a difference map and refined with free coordinates and isotropic U parameter. Other H atoms were placed in idealized positions and refined with a riding model and fixed isotropic U parameters. C—H bond lengths were fixed to 0.96 (methyl), 0.97 (methylene), or 0.98 Å (methine). Displacement parameters were calculated as Uiso(H) = xUeq(parent C) where x = 1.5 (methyl) or 1.2 (methylene, methine).
of the tosylate S atom allowed to refine a (Flack, 1983), which is in agreement with the expected for the molecule.Data collection: XSCANS (Siemens, 1996); cell
XSCANS (Siemens, 1996); data reduction: XSCANS (Siemens, 1996); 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: SHELXL97 (Sheldrick, 2008).C34H50O6S | Dx = 1.236 Mg m−3 |
Mr = 586.80 | Melting point: 422 K |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 72 reflections |
a = 6.7653 (8) Å | θ = 4.6–12.5° |
b = 12.2856 (11) Å | µ = 0.15 mm−1 |
c = 37.943 (4) Å | T = 296 K |
V = 3153.6 (6) Å3 | Prism, colourless |
Z = 4 | 0.6 × 0.5 × 0.4 mm |
F(000) = 1272 |
Bruker P4 diffractometer | 5274 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube, FN4 | Rint = 0.023 |
Graphite monochromator | θmax = 26.3°, θmin = 2.0° |
ω scans | h = −8→6 |
Absorption correction: ψ scan (XSCANS; Siemens, 1996) | k = −15→15 |
Tmin = 0.905, Tmax = 0.943 | l = −46→47 |
9218 measured reflections | 3 standard reflections every 97 reflections |
6167 independent reflections | intensity decay: 1.5% |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H atoms treated by a mixture of independent and constrained refinement |
R[F2 > 2σ(F2)] = 0.036 | w = 1/[σ2(Fo2) + (0.0359P)2 + 0.5535P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.090 | (Δ/σ)max = 0.002 |
S = 1.03 | Δρmax = 0.16 e Å−3 |
6167 reflections | Δρmin = −0.16 e Å−3 |
380 parameters | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
0 restraints | Extinction coefficient: 0.0058 (5) |
0 constraints | Absolute structure: Flack (1983), 2504 Friedel pairs |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: −0.03 (7) |
Secondary atom site location: difference Fourier map |
C34H50O6S | V = 3153.6 (6) Å3 |
Mr = 586.80 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.7653 (8) Å | µ = 0.15 mm−1 |
b = 12.2856 (11) Å | T = 296 K |
c = 37.943 (4) Å | 0.6 × 0.5 × 0.4 mm |
Bruker P4 diffractometer | 5274 reflections with I > 2σ(I) |
Absorption correction: ψ scan (XSCANS; Siemens, 1996) | Rint = 0.023 |
Tmin = 0.905, Tmax = 0.943 | 3 standard reflections every 97 reflections |
9218 measured reflections | intensity decay: 1.5% |
6167 independent reflections |
R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.090 | Δρmax = 0.16 e Å−3 |
S = 1.03 | Δρmin = −0.16 e Å−3 |
6167 reflections | Absolute structure: Flack (1983), 2504 Friedel pairs |
380 parameters | Absolute structure parameter: −0.03 (7) |
0 restraints |
x | y | z | Uiso*/Ueq | ||
C1 | 0.7277 (3) | 0.76613 (17) | 0.81367 (5) | 0.0487 (5) | |
H1A | 0.7549 | 0.7024 | 0.7994 | 0.058* | |
H1B | 0.8056 | 0.8259 | 0.8044 | 0.058* | |
C2 | 0.7923 (3) | 0.74351 (17) | 0.85158 (5) | 0.0535 (5) | |
H2A | 0.7246 | 0.6793 | 0.8603 | 0.064* | |
H2B | 0.9333 | 0.7293 | 0.8521 | 0.064* | |
C3 | 0.7455 (3) | 0.83933 (17) | 0.87512 (5) | 0.0501 (5) | |
H3A | 0.8291 | 0.9013 | 0.8686 | 0.060* | |
C4 | 0.5302 (3) | 0.87241 (18) | 0.87337 (5) | 0.0510 (5) | |
H4A | 0.5095 | 0.9374 | 0.8874 | 0.061* | |
H4B | 0.4485 | 0.8148 | 0.8830 | 0.061* | |
C5 | 0.4702 (3) | 0.89471 (15) | 0.83500 (4) | 0.0424 (4) | |
H5A | 0.5563 | 0.9532 | 0.8265 | 0.051* | |
C6 | 0.2580 (3) | 0.93700 (16) | 0.83213 (5) | 0.0478 (4) | |
H6A | 0.1664 | 0.8805 | 0.8402 | 0.057* | |
C7 | 0.2094 (3) | 0.96671 (16) | 0.79427 (5) | 0.0484 (5) | |
H7A | 0.2901 | 1.0282 | 0.7872 | 0.058* | |
H7B | 0.0720 | 0.9889 | 0.7929 | 0.058* | |
C8 | 0.2445 (3) | 0.87236 (14) | 0.76861 (4) | 0.0392 (4) | |
H8A | 0.1540 | 0.8130 | 0.7748 | 0.047* | |
C9 | 0.4581 (3) | 0.82992 (14) | 0.77203 (4) | 0.0397 (4) | |
H9A | 0.5443 | 0.8920 | 0.7668 | 0.048* | |
C10 | 0.5071 (3) | 0.79483 (14) | 0.81045 (4) | 0.0398 (4) | |
C11 | 0.5084 (3) | 0.74214 (17) | 0.74437 (5) | 0.0520 (5) | |
H11A | 0.6494 | 0.7280 | 0.7451 | 0.062* | |
H11B | 0.4410 | 0.6752 | 0.7507 | 0.062* | |
C12 | 0.4505 (3) | 0.77331 (17) | 0.70650 (5) | 0.0493 (5) | |
H12A | 0.5339 | 0.8326 | 0.6985 | 0.059* | |
H12B | 0.4723 | 0.7116 | 0.6910 | 0.059* | |
C13 | 0.2344 (3) | 0.80791 (14) | 0.70437 (4) | 0.0392 (4) | |
C14 | 0.2068 (3) | 0.90418 (14) | 0.73031 (4) | 0.0394 (4) | |
H14A | 0.3094 | 0.9573 | 0.7243 | 0.047* | |
C15 | 0.0107 (3) | 0.95550 (16) | 0.71905 (5) | 0.0487 (4) | |
H15A | −0.0063 | 1.0275 | 0.7291 | 0.058* | |
H15B | −0.1011 | 0.9102 | 0.7255 | 0.058* | |
C16 | 0.0397 (3) | 0.96013 (15) | 0.67900 (4) | 0.0444 (4) | |
H16A | 0.1065 | 1.0281 | 0.6726 | 0.053* | |
C17 | 0.1717 (3) | 0.86180 (14) | 0.66890 (4) | 0.0409 (4) | |
H17A | 0.2900 | 0.8885 | 0.6567 | 0.049* | |
C18 | 0.1006 (3) | 0.71110 (16) | 0.71335 (5) | 0.0555 (5) | |
H18A | 0.1350 | 0.6833 | 0.7362 | 0.083* | |
H18B | 0.1178 | 0.6550 | 0.6960 | 0.083* | |
H18C | −0.0348 | 0.7344 | 0.7135 | 0.083* | |
C19 | 0.3831 (3) | 0.69510 (15) | 0.82133 (5) | 0.0517 (5) | |
H19A | 0.4338 | 0.6313 | 0.8099 | 0.078* | |
H19B | 0.2480 | 0.7062 | 0.8145 | 0.078* | |
H19C | 0.3902 | 0.6858 | 0.8464 | 0.078* | |
C20 | 0.0414 (3) | 0.79983 (16) | 0.64246 (5) | 0.0483 (5) | |
H20A | −0.0400 | 0.7484 | 0.6558 | 0.058* | |
C21 | 0.1537 (4) | 0.7352 (2) | 0.61469 (6) | 0.0721 (7) | |
H21A | 0.0614 | 0.7007 | 0.5991 | 0.108* | |
H21B | 0.2333 | 0.6808 | 0.6260 | 0.108* | |
H21C | 0.2373 | 0.7834 | 0.6015 | 0.108* | |
C22 | −0.0941 (3) | 0.88812 (16) | 0.62844 (4) | 0.0471 (4) | |
C23 | −0.2867 (3) | 0.85149 (19) | 0.61189 (5) | 0.0588 (5) | |
H23A | −0.3665 | 0.8151 | 0.6296 | 0.071* | |
H23B | −0.2587 | 0.7995 | 0.5933 | 0.071* | |
C24 | −0.4025 (4) | 0.9461 (2) | 0.59666 (6) | 0.0648 (6) | |
H24A | −0.5165 | 0.9185 | 0.5840 | 0.078* | |
H24B | −0.4499 | 0.9918 | 0.6157 | 0.078* | |
C25 | −0.2772 (4) | 1.01361 (18) | 0.57190 (5) | 0.0593 (5) | |
H25A | −0.2429 | 0.9686 | 0.5515 | 0.071* | |
C26 | −0.0883 (4) | 1.04441 (18) | 0.59073 (5) | 0.0599 (5) | |
H26A | −0.0032 | 1.0834 | 0.5745 | 0.072* | |
H26B | −0.1198 | 1.0932 | 0.6100 | 0.072* | |
O27 | 0.0167 (2) | 0.95231 (12) | 0.60433 (3) | 0.0537 (3) | |
C28 | −0.3833 (4) | 1.1154 (2) | 0.55875 (6) | 0.0824 (7) | |
H28A | −0.2911 | 1.1613 | 0.5465 | 0.124* | |
H28B | −0.4377 | 1.1543 | 0.5784 | 0.124* | |
H28C | −0.4878 | 1.0948 | 0.5430 | 0.124* | |
O29 | −0.1410 (2) | 0.95014 (11) | 0.65939 (3) | 0.0510 (3) | |
O30 | 0.2301 (3) | 1.03360 (13) | 0.85290 (4) | 0.0693 (5) | |
H30 | 0.206 (5) | 1.017 (3) | 0.8723 (8) | 0.107 (12)* | |
O31 | 0.7980 (2) | 0.80181 (12) | 0.91112 (3) | 0.0565 (4) | |
S32 | 0.89495 (8) | 0.88025 (5) | 0.938758 (13) | 0.05819 (15) | |
O33 | 1.0188 (2) | 0.95749 (16) | 0.92101 (4) | 0.0753 (5) | |
O34 | 0.9767 (3) | 0.80926 (16) | 0.96460 (4) | 0.0825 (5) | |
C35 | 0.6942 (3) | 0.94918 (16) | 0.95735 (5) | 0.0506 (5) | |
C36 | 0.6646 (4) | 1.05871 (19) | 0.95077 (7) | 0.0735 (7) | |
H36A | 0.7537 | 1.0974 | 0.9369 | 0.088* | |
C37 | 0.5013 (5) | 1.1100 (2) | 0.96490 (8) | 0.0859 (8) | |
H37A | 0.4812 | 1.1834 | 0.9601 | 0.103* | |
C38 | 0.3682 (4) | 1.0562 (2) | 0.98576 (7) | 0.0763 (7) | |
C39 | 0.4014 (4) | 0.9468 (2) | 0.99195 (6) | 0.0749 (7) | |
H39A | 0.3125 | 0.9084 | 1.0059 | 0.090* | |
C40 | 0.5620 (3) | 0.89296 (19) | 0.97808 (5) | 0.0614 (6) | |
H40A | 0.5811 | 0.8193 | 0.9827 | 0.074* | |
C41 | 0.1927 (6) | 1.1145 (3) | 1.00114 (11) | 0.1337 (14) | |
H41A | 0.1886 | 1.1877 | 0.9923 | 0.201* | |
H41B | 0.2040 | 1.1160 | 1.0264 | 0.201* | |
H41C | 0.0737 | 1.0771 | 0.9946 | 0.201* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0473 (11) | 0.0556 (11) | 0.0431 (10) | 0.0123 (9) | 0.0071 (9) | 0.0001 (9) |
C2 | 0.0517 (12) | 0.0623 (12) | 0.0465 (10) | 0.0189 (10) | 0.0007 (9) | 0.0011 (9) |
C3 | 0.0565 (12) | 0.0576 (11) | 0.0362 (9) | 0.0088 (10) | −0.0011 (9) | 0.0058 (8) |
C4 | 0.0581 (12) | 0.0573 (11) | 0.0378 (9) | 0.0136 (10) | 0.0044 (8) | 0.0005 (9) |
C5 | 0.0475 (10) | 0.0443 (9) | 0.0355 (8) | 0.0061 (9) | 0.0048 (8) | 0.0013 (7) |
C6 | 0.0553 (11) | 0.0487 (10) | 0.0394 (9) | 0.0171 (9) | 0.0063 (9) | −0.0048 (8) |
C7 | 0.0552 (12) | 0.0494 (10) | 0.0407 (9) | 0.0202 (10) | 0.0017 (8) | −0.0024 (8) |
C8 | 0.0428 (10) | 0.0393 (9) | 0.0356 (8) | 0.0050 (8) | 0.0057 (7) | −0.0007 (7) |
C9 | 0.0406 (10) | 0.0420 (9) | 0.0367 (8) | 0.0025 (8) | 0.0077 (7) | 0.0027 (7) |
C10 | 0.0411 (10) | 0.0416 (9) | 0.0369 (8) | 0.0078 (8) | 0.0084 (8) | 0.0022 (7) |
C11 | 0.0537 (11) | 0.0586 (11) | 0.0436 (10) | 0.0190 (10) | 0.0077 (9) | −0.0053 (9) |
C12 | 0.0533 (12) | 0.0549 (11) | 0.0397 (9) | 0.0111 (10) | 0.0076 (8) | −0.0040 (9) |
C13 | 0.0441 (10) | 0.0369 (8) | 0.0366 (8) | −0.0013 (8) | 0.0069 (8) | −0.0022 (7) |
C14 | 0.0446 (10) | 0.0357 (9) | 0.0380 (8) | −0.0003 (8) | 0.0050 (8) | −0.0008 (7) |
C15 | 0.0578 (12) | 0.0491 (10) | 0.0393 (9) | 0.0138 (10) | −0.0017 (9) | −0.0074 (8) |
C16 | 0.0529 (11) | 0.0416 (9) | 0.0387 (9) | −0.0013 (9) | −0.0036 (8) | −0.0019 (8) |
C17 | 0.0439 (10) | 0.0418 (9) | 0.0371 (8) | −0.0051 (8) | 0.0046 (7) | −0.0016 (7) |
C18 | 0.0685 (13) | 0.0443 (10) | 0.0536 (11) | −0.0121 (11) | 0.0078 (11) | 0.0016 (9) |
C19 | 0.0589 (12) | 0.0464 (10) | 0.0498 (10) | 0.0020 (10) | 0.0090 (10) | 0.0082 (9) |
C20 | 0.0554 (12) | 0.0471 (10) | 0.0424 (9) | −0.0055 (9) | 0.0033 (8) | −0.0089 (8) |
C21 | 0.0797 (17) | 0.0773 (16) | 0.0594 (13) | 0.0107 (14) | −0.0034 (12) | −0.0307 (12) |
C22 | 0.0501 (10) | 0.0540 (10) | 0.0373 (8) | −0.0082 (10) | 0.0034 (8) | −0.0058 (8) |
C23 | 0.0579 (13) | 0.0719 (14) | 0.0468 (11) | −0.0172 (12) | −0.0006 (10) | −0.0029 (10) |
C24 | 0.0556 (13) | 0.0872 (16) | 0.0516 (11) | −0.0077 (14) | −0.0082 (10) | −0.0018 (11) |
C25 | 0.0699 (14) | 0.0672 (13) | 0.0409 (10) | −0.0005 (12) | −0.0053 (10) | −0.0072 (9) |
C26 | 0.0707 (14) | 0.0584 (12) | 0.0506 (11) | −0.0120 (12) | −0.0046 (11) | 0.0041 (10) |
O27 | 0.0522 (8) | 0.0616 (8) | 0.0472 (7) | −0.0106 (7) | 0.0010 (6) | 0.0036 (7) |
C28 | 0.0959 (19) | 0.0858 (17) | 0.0654 (14) | 0.0142 (17) | −0.0129 (14) | 0.0027 (14) |
O29 | 0.0533 (8) | 0.0609 (8) | 0.0387 (6) | 0.0071 (7) | −0.0027 (6) | −0.0085 (6) |
O30 | 0.0981 (13) | 0.0661 (9) | 0.0435 (8) | 0.0378 (10) | 0.0019 (9) | −0.0110 (7) |
O31 | 0.0708 (10) | 0.0598 (8) | 0.0390 (6) | 0.0138 (8) | −0.0043 (6) | 0.0051 (6) |
S32 | 0.0559 (3) | 0.0777 (4) | 0.0410 (2) | 0.0079 (3) | −0.0039 (2) | 0.0055 (2) |
O33 | 0.0600 (9) | 0.1110 (13) | 0.0551 (9) | −0.0139 (10) | 0.0071 (8) | 0.0017 (9) |
O34 | 0.0882 (12) | 0.1071 (13) | 0.0521 (8) | 0.0312 (11) | −0.0188 (9) | 0.0102 (9) |
C35 | 0.0605 (12) | 0.0548 (11) | 0.0365 (9) | −0.0038 (10) | 0.0006 (9) | 0.0038 (9) |
C36 | 0.0881 (19) | 0.0585 (13) | 0.0740 (15) | −0.0034 (13) | 0.0191 (13) | 0.0177 (12) |
C37 | 0.108 (2) | 0.0530 (13) | 0.0968 (18) | 0.0096 (16) | 0.0092 (18) | 0.0002 (14) |
C38 | 0.0751 (17) | 0.0809 (17) | 0.0730 (15) | 0.0027 (15) | 0.0090 (13) | −0.0160 (14) |
C39 | 0.0727 (16) | 0.0827 (17) | 0.0692 (14) | −0.0126 (15) | 0.0197 (13) | 0.0031 (13) |
C40 | 0.0720 (15) | 0.0563 (12) | 0.0559 (11) | −0.0085 (12) | 0.0084 (11) | 0.0065 (10) |
C41 | 0.117 (3) | 0.134 (3) | 0.150 (3) | 0.031 (3) | 0.041 (3) | −0.040 (3) |
C1—C2 | 1.528 (3) | C18—H18B | 0.9600 |
C1—C10 | 1.539 (3) | C18—H18C | 0.9600 |
C1—H1A | 0.9700 | C19—H19A | 0.9600 |
C1—H1B | 0.9700 | C19—H19B | 0.9600 |
C2—C3 | 1.511 (3) | C19—H19C | 0.9600 |
C2—H2A | 0.9700 | C20—C22 | 1.516 (3) |
C2—H2B | 0.9700 | C20—C21 | 1.523 (3) |
C3—O31 | 1.485 (2) | C20—H20A | 0.9800 |
C3—C4 | 1.514 (3) | C21—H21A | 0.9600 |
C3—H3A | 0.9800 | C21—H21B | 0.9600 |
C4—C5 | 1.536 (2) | C21—H21C | 0.9600 |
C4—H4A | 0.9700 | C22—O27 | 1.422 (2) |
C4—H4B | 0.9700 | C22—O29 | 1.435 (2) |
C5—C6 | 1.530 (3) | C22—C23 | 1.515 (3) |
C5—C10 | 1.561 (2) | C23—C24 | 1.516 (3) |
C5—H5A | 0.9800 | C23—H23A | 0.9700 |
C6—O30 | 1.437 (2) | C23—H23B | 0.9700 |
C6—C7 | 1.518 (2) | C24—C25 | 1.513 (3) |
C6—H6A | 0.9800 | C24—H24A | 0.9700 |
C7—C8 | 1.532 (2) | C24—H24B | 0.9700 |
C7—H7A | 0.9700 | C25—C26 | 1.512 (3) |
C7—H7B | 0.9700 | C25—C28 | 1.526 (3) |
C8—C14 | 1.526 (2) | C25—H25A | 0.9800 |
C8—C9 | 1.542 (2) | C26—O27 | 1.432 (3) |
C8—H8A | 0.9800 | C26—H26A | 0.9700 |
C9—C11 | 1.543 (2) | C26—H26B | 0.9700 |
C9—C10 | 1.556 (2) | C28—H28A | 0.9600 |
C9—H9A | 0.9800 | C28—H28B | 0.9600 |
C10—C19 | 1.541 (3) | C28—H28C | 0.9600 |
C11—C12 | 1.538 (3) | O30—H30 | 0.78 (3) |
C11—H11A | 0.9700 | O31—S32 | 1.5680 (15) |
C11—H11B | 0.9700 | S32—O34 | 1.4241 (16) |
C12—C13 | 1.525 (3) | S32—O33 | 1.4340 (18) |
C12—H12A | 0.9700 | S32—C35 | 1.749 (2) |
C12—H12B | 0.9700 | C35—C40 | 1.377 (3) |
C13—C18 | 1.533 (3) | C35—C36 | 1.383 (3) |
C13—C14 | 1.550 (2) | C36—C37 | 1.380 (4) |
C13—C17 | 1.559 (2) | C36—H36A | 0.9300 |
C14—C15 | 1.529 (3) | C37—C38 | 1.369 (4) |
C14—H14A | 0.9800 | C37—H37A | 0.9300 |
C15—C16 | 1.533 (2) | C38—C39 | 1.383 (4) |
C15—H15A | 0.9700 | C38—C41 | 1.504 (4) |
C15—H15B | 0.9700 | C39—C40 | 1.377 (3) |
C16—O29 | 1.436 (2) | C39—H39A | 0.9300 |
C16—C17 | 1.550 (3) | C40—H40A | 0.9300 |
C16—H16A | 0.9800 | C41—H41A | 0.9600 |
C17—C20 | 1.537 (3) | C41—H41B | 0.9600 |
C17—H17A | 0.9800 | C41—H41C | 0.9600 |
C18—H18A | 0.9600 | ||
C2—C1—C10 | 113.18 (16) | C16—C17—C13 | 105.90 (13) |
C2—C1—H1A | 108.9 | C20—C17—H17A | 109.1 |
C10—C1—H1A | 108.9 | C16—C17—H17A | 109.1 |
C2—C1—H1B | 108.9 | C13—C17—H17A | 109.1 |
C10—C1—H1B | 108.9 | C13—C18—H18A | 109.5 |
H1A—C1—H1B | 107.8 | C13—C18—H18B | 109.5 |
C3—C2—C1 | 110.78 (16) | H18A—C18—H18B | 109.5 |
C3—C2—H2A | 109.5 | C13—C18—H18C | 109.5 |
C1—C2—H2A | 109.5 | H18A—C18—H18C | 109.5 |
C3—C2—H2B | 109.5 | H18B—C18—H18C | 109.5 |
C1—C2—H2B | 109.5 | C10—C19—H19A | 109.5 |
H2A—C2—H2B | 108.1 | C10—C19—H19B | 109.5 |
O31—C3—C2 | 104.59 (15) | H19A—C19—H19B | 109.5 |
O31—C3—C4 | 110.72 (16) | C10—C19—H19C | 109.5 |
C2—C3—C4 | 112.62 (18) | H19A—C19—H19C | 109.5 |
O31—C3—H3A | 109.6 | H19B—C19—H19C | 109.5 |
C2—C3—H3A | 109.6 | C22—C20—C21 | 115.60 (17) |
C4—C3—H3A | 109.6 | C22—C20—C17 | 102.79 (15) |
C3—C4—C5 | 110.11 (15) | C21—C20—C17 | 115.06 (18) |
C3—C4—H4A | 109.6 | C22—C20—H20A | 107.6 |
C5—C4—H4A | 109.6 | C21—C20—H20A | 107.6 |
C3—C4—H4B | 109.6 | C17—C20—H20A | 107.6 |
C5—C4—H4B | 109.6 | C20—C21—H21A | 109.5 |
H4A—C4—H4B | 108.2 | C20—C21—H21B | 109.5 |
C6—C5—C4 | 112.09 (15) | H21A—C21—H21B | 109.5 |
C6—C5—C10 | 112.00 (15) | C20—C21—H21C | 109.5 |
C4—C5—C10 | 112.53 (15) | H21A—C21—H21C | 109.5 |
C6—C5—H5A | 106.6 | H21B—C21—H21C | 109.5 |
C4—C5—H5A | 106.6 | O27—C22—O29 | 110.39 (15) |
C10—C5—H5A | 106.6 | O27—C22—C23 | 110.60 (16) |
O30—C6—C7 | 106.97 (15) | O29—C22—C23 | 107.87 (16) |
O30—C6—C5 | 111.38 (17) | O27—C22—C20 | 107.67 (16) |
C7—C6—C5 | 110.63 (15) | O29—C22—C20 | 103.08 (14) |
O30—C6—H6A | 109.3 | C23—C22—C20 | 116.93 (18) |
C7—C6—H6A | 109.3 | C22—C23—C24 | 111.99 (18) |
C5—C6—H6A | 109.3 | C22—C23—H23A | 109.2 |
C6—C7—C8 | 112.68 (15) | C24—C23—H23A | 109.2 |
C6—C7—H7A | 109.1 | C22—C23—H23B | 109.2 |
C8—C7—H7A | 109.1 | C24—C23—H23B | 109.2 |
C6—C7—H7B | 109.1 | H23A—C23—H23B | 107.9 |
C8—C7—H7B | 109.1 | C25—C24—C23 | 111.6 (2) |
H7A—C7—H7B | 107.8 | C25—C24—H24A | 109.3 |
C14—C8—C7 | 112.66 (14) | C23—C24—H24A | 109.3 |
C14—C8—C9 | 108.86 (14) | C25—C24—H24B | 109.3 |
C7—C8—C9 | 110.35 (15) | C23—C24—H24B | 109.3 |
C14—C8—H8A | 108.3 | H24A—C24—H24B | 108.0 |
C7—C8—H8A | 108.3 | C26—C25—C24 | 108.51 (17) |
C9—C8—H8A | 108.3 | C26—C25—C28 | 110.3 (2) |
C8—C9—C11 | 112.69 (16) | C24—C25—C28 | 112.9 (2) |
C8—C9—C10 | 111.83 (14) | C26—C25—H25A | 108.3 |
C11—C9—C10 | 113.38 (15) | C24—C25—H25A | 108.3 |
C8—C9—H9A | 106.1 | C28—C25—H25A | 108.3 |
C11—C9—H9A | 106.1 | O27—C26—C25 | 113.06 (17) |
C10—C9—H9A | 106.1 | O27—C26—H26A | 109.0 |
C1—C10—C19 | 108.94 (16) | C25—C26—H26A | 109.0 |
C1—C10—C9 | 110.15 (14) | O27—C26—H26B | 109.0 |
C19—C10—C9 | 110.82 (16) | C25—C26—H26B | 109.0 |
C1—C10—C5 | 106.74 (16) | H26A—C26—H26B | 107.8 |
C19—C10—C5 | 112.22 (14) | C22—O27—C26 | 114.12 (16) |
C9—C10—C5 | 107.90 (14) | C25—C28—H28A | 109.5 |
C12—C11—C9 | 113.93 (15) | C25—C28—H28B | 109.5 |
C12—C11—H11A | 108.8 | H28A—C28—H28B | 109.5 |
C9—C11—H11A | 108.8 | C25—C28—H28C | 109.5 |
C12—C11—H11B | 108.8 | H28A—C28—H28C | 109.5 |
C9—C11—H11B | 108.8 | H28B—C28—H28C | 109.5 |
H11A—C11—H11B | 107.7 | C22—O29—C16 | 106.34 (13) |
C13—C12—C11 | 111.28 (15) | C6—O30—H30 | 109 (2) |
C13—C12—H12A | 109.4 | C3—O31—S32 | 121.63 (13) |
C11—C12—H12A | 109.4 | O34—S32—O33 | 120.11 (12) |
C13—C12—H12B | 109.4 | O34—S32—O31 | 104.27 (10) |
C11—C12—H12B | 109.4 | O33—S32—O31 | 109.71 (9) |
H12A—C12—H12B | 108.0 | O34—S32—C35 | 108.69 (10) |
C12—C13—C18 | 109.76 (16) | O33—S32—C35 | 108.83 (11) |
C12—C13—C14 | 107.14 (15) | O31—S32—C35 | 104.03 (9) |
C18—C13—C14 | 112.31 (14) | C40—C35—C36 | 119.8 (2) |
C12—C13—C17 | 115.15 (15) | C40—C35—S32 | 119.47 (16) |
C18—C13—C17 | 111.15 (16) | C36—C35—S32 | 120.73 (17) |
C14—C13—C17 | 101.04 (13) | C37—C36—C35 | 119.4 (2) |
C8—C14—C15 | 121.10 (15) | C37—C36—H36A | 120.3 |
C8—C14—C13 | 112.90 (14) | C35—C36—H36A | 120.3 |
C15—C14—C13 | 103.99 (14) | C38—C37—C36 | 122.1 (2) |
C8—C14—H14A | 105.9 | C38—C37—H37A | 119.0 |
C15—C14—H14A | 105.9 | C36—C37—H37A | 119.0 |
C13—C14—H14A | 105.9 | C37—C38—C39 | 117.4 (2) |
C14—C15—C16 | 100.44 (15) | C37—C38—C41 | 120.9 (3) |
C14—C15—H15A | 111.7 | C39—C38—C41 | 121.7 (3) |
C16—C15—H15A | 111.7 | C40—C39—C38 | 122.0 (2) |
C14—C15—H15B | 111.7 | C40—C39—H39A | 119.0 |
C16—C15—H15B | 111.7 | C38—C39—H39A | 119.0 |
H15A—C15—H15B | 109.5 | C39—C40—C35 | 119.4 (2) |
O29—C16—C15 | 113.67 (16) | C39—C40—H40A | 120.3 |
O29—C16—C17 | 107.18 (14) | C35—C40—H40A | 120.3 |
C15—C16—C17 | 106.85 (14) | C38—C41—H41A | 109.5 |
O29—C16—H16A | 109.7 | C38—C41—H41B | 109.5 |
C15—C16—H16A | 109.7 | H41A—C41—H41B | 109.5 |
C17—C16—H16A | 109.7 | C38—C41—H41C | 109.5 |
C20—C17—C16 | 102.53 (15) | H41A—C41—H41C | 109.5 |
C20—C17—C13 | 120.61 (15) | H41B—C41—H41C | 109.5 |
C10—C1—C2—C3 | −56.5 (2) | O29—C16—C17—C13 | −127.69 (15) |
C1—C2—C3—O31 | 174.77 (17) | C15—C16—C17—C13 | −5.49 (19) |
C1—C2—C3—C4 | 54.5 (2) | C12—C13—C17—C20 | 107.2 (2) |
O31—C3—C4—C5 | −171.61 (16) | C18—C13—C17—C20 | −18.4 (2) |
C2—C3—C4—C5 | −54.9 (2) | C14—C13—C17—C20 | −137.79 (17) |
C3—C4—C5—C6 | −175.57 (17) | C12—C13—C17—C16 | −137.32 (16) |
C3—C4—C5—C10 | 57.1 (2) | C18—C13—C17—C16 | 97.08 (17) |
C4—C5—C6—O30 | 56.6 (2) | C14—C13—C17—C16 | −22.27 (17) |
C10—C5—C6—O30 | −175.81 (15) | C16—C17—C20—C22 | 24.43 (18) |
C4—C5—C6—C7 | 175.44 (17) | C13—C17—C20—C22 | 141.67 (16) |
C10—C5—C6—C7 | −57.0 (2) | C16—C17—C20—C21 | 150.96 (18) |
O30—C6—C7—C8 | 176.66 (17) | C13—C17—C20—C21 | −91.8 (2) |
C5—C6—C7—C8 | 55.2 (2) | C21—C20—C22—O27 | −50.2 (2) |
C6—C7—C8—C14 | −176.75 (17) | C17—C20—C22—O27 | 76.01 (17) |
C6—C7—C8—C9 | −54.8 (2) | C21—C20—C22—O29 | −166.88 (18) |
C14—C8—C9—C11 | −50.40 (19) | C17—C20—C22—O29 | −40.70 (18) |
C7—C8—C9—C11 | −174.53 (15) | C21—C20—C22—C23 | 75.0 (2) |
C14—C8—C9—C10 | −179.51 (15) | C17—C20—C22—C23 | −158.82 (16) |
C7—C8—C9—C10 | 56.36 (19) | O27—C22—C23—C24 | −52.4 (2) |
C2—C1—C10—C19 | −64.9 (2) | O29—C22—C23—C24 | 68.4 (2) |
C2—C1—C10—C9 | 173.36 (16) | C20—C22—C23—C24 | −176.07 (17) |
C2—C1—C10—C5 | 56.5 (2) | C22—C23—C24—C25 | 52.5 (2) |
C8—C9—C10—C1 | −173.24 (15) | C23—C24—C25—C26 | −52.1 (2) |
C11—C9—C10—C1 | 58.0 (2) | C23—C24—C25—C28 | −174.71 (18) |
C8—C9—C10—C19 | 66.14 (19) | C24—C25—C26—O27 | 54.8 (2) |
C11—C9—C10—C19 | −62.6 (2) | C28—C25—C26—O27 | 178.89 (18) |
C8—C9—C10—C5 | −57.08 (19) | O29—C22—O27—C26 | −63.9 (2) |
C11—C9—C10—C5 | 174.17 (16) | C23—C22—O27—C26 | 55.4 (2) |
C6—C5—C10—C1 | 175.76 (15) | C20—C22—O27—C26 | −175.73 (15) |
C4—C5—C10—C1 | −56.9 (2) | C25—C26—O27—C22 | −58.3 (2) |
C6—C5—C10—C19 | −65.0 (2) | O27—C22—O29—C16 | −73.14 (18) |
C4—C5—C10—C19 | 62.4 (2) | C23—C22—O29—C16 | 165.92 (16) |
C6—C5—C10—C9 | 57.39 (19) | C20—C22—O29—C16 | 41.62 (18) |
C4—C5—C10—C9 | −175.26 (16) | C15—C16—O29—C22 | −143.50 (16) |
C8—C9—C11—C12 | 48.6 (2) | C17—C16—O29—C22 | −25.66 (18) |
C10—C9—C11—C12 | 176.91 (17) | C2—C3—O31—S32 | 142.58 (15) |
C9—C11—C12—C13 | −52.6 (2) | C4—C3—O31—S32 | −95.9 (2) |
C11—C12—C13—C18 | −64.8 (2) | C3—O31—S32—O34 | −162.55 (15) |
C11—C12—C13—C14 | 57.4 (2) | C3—O31—S32—O33 | −32.69 (18) |
C11—C12—C13—C17 | 168.88 (15) | C3—O31—S32—C35 | 83.60 (16) |
C7—C8—C14—C15 | −53.7 (2) | O34—S32—C35—C40 | −42.7 (2) |
C9—C8—C14—C15 | −176.44 (16) | O33—S32—C35—C40 | −175.16 (17) |
C7—C8—C14—C13 | −177.83 (15) | O31—S32—C35—C40 | 67.93 (18) |
C9—C8—C14—C13 | 59.4 (2) | O34—S32—C35—C36 | 138.8 (2) |
C12—C13—C14—C8 | −63.21 (19) | O33—S32—C35—C36 | 6.4 (2) |
C18—C13—C14—C8 | 57.4 (2) | O31—S32—C35—C36 | −110.5 (2) |
C17—C13—C14—C8 | 175.91 (15) | C40—C35—C36—C37 | −0.5 (4) |
C12—C13—C14—C15 | 163.71 (15) | S32—C35—C36—C37 | 177.9 (2) |
C18—C13—C14—C15 | −75.69 (18) | C35—C36—C37—C38 | 0.9 (4) |
C17—C13—C14—C15 | 42.83 (17) | C36—C37—C38—C39 | −0.8 (4) |
C8—C14—C15—C16 | −174.43 (16) | C36—C37—C38—C41 | 179.3 (3) |
C13—C14—C15—C16 | −46.22 (17) | C37—C38—C39—C40 | 0.4 (4) |
C14—C15—C16—O29 | 149.34 (15) | C41—C38—C39—C40 | −179.7 (3) |
C14—C15—C16—C17 | 31.31 (18) | C38—C39—C40—C35 | −0.1 (4) |
O29—C16—C17—C20 | −0.41 (18) | C36—C35—C40—C39 | 0.1 (3) |
C15—C16—C17—C20 | 121.79 (16) | S32—C35—C40—C39 | −178.35 (18) |
D—H···A | D—H | H···A | D···A | D—H···A |
O30—H30···O33i | 0.78 (3) | 2.35 (3) | 3.098 (2) | 159 (3) |
C40—H40A···O34ii | 0.93 | 2.65 | 3.352 (3) | 133 |
Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+3/2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C34H50O6S |
Mr | 586.80 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 296 |
a, b, c (Å) | 6.7653 (8), 12.2856 (11), 37.943 (4) |
V (Å3) | 3153.6 (6) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.15 |
Crystal size (mm) | 0.6 × 0.5 × 0.4 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | ψ scan (XSCANS; Siemens, 1996) |
Tmin, Tmax | 0.905, 0.943 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9218, 6167, 5274 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.622 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.090, 1.03 |
No. of reflections | 6167 |
No. of parameters | 380 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.16, −0.16 |
Absolute structure | Flack (1983), 2504 Friedel pairs |
Absolute structure parameter | −0.03 (7) |
Computer programs: XSCANS (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O30—H30···O33i | 0.78 (3) | 2.35 (3) | 3.098 (2) | 159 (3) |
C40—H40A···O34ii | 0.93 | 2.65 | 3.352 (3) | 133.3 |
Symmetry codes: (i) x−1, y, z; (ii) x−1/2, −y+3/2, −z+2. |
Acknowledgements
The authors thank CONACYT for the Repatriation grant 166040 and PROMEP for the grant PROMEP/103.5/12/4367 BUAP-PTC-301.
References
Asami, T., Nakano, T. & Fujioka, S. (2005). Vitam. Horm. 72, 479–504. 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.
Brassinosteroids (BS) are endogenous plant hormones essential for the regulation of multiple physiological processes required for normal plant growth and development (Asami et al., 2005). Since their discovery, more than 30 years ago, the synthetic chemistry has been extensively developed for obtaining BS and analogs (Zullo & Adam, 2002; Kang & Guo, 2011). The most active BS and analogs possess a 2α,3α-diol in ring A and a ketone at C-6 (or a lactone) in ring B. The introduction of the required 6-keto-2α,3α-diol functionality has been satisfactorily achieved from the 6-hydroxy-3β-tosylate framework. The title compound belongs to this line of synthetic approaches to BS analogs. It was synthesized from diosgenin, through a tosylation followed by hydroboration-oxidation (Smith & Pelter, 1991; Brown, 1962). Commonly, the crude product after the hydroboration-oxidation procedure is immediately oxidized in order to obtain the 6-keto derivative; we decided instead, to isolate and properly characterize the 6-hydroxy intermediate.
The compound crystallizes with one molecule in the asymmetric unit (Fig. 1) and the conformation of the A-F ring system is as expected for a spirostan nucleus. All 6-membered rings have a chair conformation, while 5-membered rings D and E are envelopes on C14 and C22, respectively. The tosylate group in equatorial position at C3 is oriented in such a way that a potential intramolecular stabilizing O—H···π contact could be formed between the hydroxyl group at C6 and the benzene ring of the tosylate. However, this interaction should have an energy approaching zero, because of the too long H···π separation, ca. 4.4 Å. On the other hand, the tosylate orientation in the title compound is similar to that observed in cholesteryl tosylate (Cox et al., 1996), which has C-6 engaged in a double bond. This suggests that the tosylate orientation results from packing restraints or intermolecular interactions rather than intramolecular contacts.
Regarding the crystal structure, the single feature of interest is the intermolecular hydrogen bond formed between the hydroxyl group and one S═O group in the tosylate. These contacts link molecules in chains oriented in the [100] direction in the crystal. A weak hydrogen bond involving the other S═O group is observed between chains, C40—H40A···O34, characterized by a small C—H···O angle of 133° (Fig. 2).