organic compounds
R,3S,4R,5R)-5-(1,3-dithian-2-yl)-3-methyl-1-(triisopropylsilyloxy)hexane-2,4-diol
of (−)-(2aUniversity of Puerto Rico, Rio Piedras Campus, Department of Chemistry, PO Box 23346, San Juan, 000936-8377, Puerto Rico
*Correspondence e-mail: jose.prieto2@upr.edu
The title compound, C20H42O3S2Si, crystallized with two independent molecules (A and B) in the They consist of syn,anti,anti-stereotetrads with a 1,3-dithiane motif and a primary alcohol protected as the triisopropyl silyl ether. The 1,3-dithiane ring adopts a chair conformation, while the rest of each molecule displays a common zigzag conformation. There is an intramolecular O—H⋯O hydrogen bond in each molecule. In the crystal, the A and B molecules are linked via O—H⋯O hydrogen bonds, forming –A–B–A--B-- chains along [010]. The was determined by (anomalous scattering) [Flack parameter = 0.035 (8)].
Keywords: crystal structure; polypropionate; stereotetrads; 1,3-dithiane.
CCDC reference: 1029553
1. Related literature
The title compound was obtained as part of our studies toward the synthesis of (+)-crocacin C, using an epoxide-based approach for the stereotetrad construction. For the one- and two-dimensional NMR spectra of the acetonide product, see: Rychnovsky & Skalitzky (1990). For the isolation and biological activity of crocacin, see: Kunze et al. (1994); Jansen et al. (1999). For the dithiane epoxide cleavage, see: Ide & Nakata (1999); Ide et al. (1999). For polypropionate-related synthesis and background, see: Li & Menche (2009); Rodríguez-Berríos et al. (2011); Torres et al. (2009); Dávila et al. (2007); Rodríguez et al. (2006). For biological activities of polypropionates, see; Li & Menche (2009); Rohr (2000). For a related structure, see: Valentín et al. (2012).
2. Experimental
2.1. Crystal data
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2.3. Refinement
Data collection: APEX2 (Bruker, 2012); cell SAINT (Bruker, 2012); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).
Supporting information
CCDC reference: 1029553
10.1107/S160053681402443X/su5013sup1.cif
contains datablocks I, New_Global_Publ_Block. DOI:Structure factors: contains datablock I. DOI: 10.1107/S160053681402443X/su5013Isup2.hkl
Supporting information file. DOI: 10.1107/S160053681402443X/su5013Isup3.cml
The synthesis of the title compound is illustrated in Fig. 3. It was synthesized using Nakata's modified protocol (Ide et al., 1999). To a flame-dried round bottom flask was added 12 mL of t-butyllithium (19.8 mmol, 1.7 M in pentane) and 4.95 mL of di-n-butylmagnesium (4.95 mmol, 1.0 M in heptane) at rt. The mixed reagents were then transferred via cannula to another flame-dried round bottom flask containing a stirred solution of 1,3-dithiane (0.99 g, 8.25 mmol) in dry THF (16 mL) at rt. The reaction mixture turned bright yellow, and was left stirring for 1 hr after which the epoxide was added (1.0 g, 3.30 mmol). After 20 h at rt, the reaction was quenched by adding saturated aqueous NH4Cl, and the resulting mixture was extracted with ethyl acetate. The combined organic phase was washed with brine, dried over MgSO4, and concentrated under reduced pressure. The resulting dithiane was purified using δ 4.76 (d, J = 2.6 Hz, 1H), 4.05 (dddd, J = 7.4, 5.5, 1.9, 1.9 Hz, 1H), 3.67 (dd, J = 9.6, 7.6 Hz, 1H), 3.60 (ddd, J = 10.1, 7.8, 2.8 Hz, 1H), 3.56 (dd, J = 9.6, 5.5 Hz, 1H), 3.32 (d, J = 7.9 Hz, 1H), 3.04 (ddd, J = 13.8, 12.6, 2.5 Hz, 1H), 2.95 – 2.80 (m, 3H), 2.85 (d, J = 7.4 Hz, 1H), 2.15 (m, 1H), 2.11 (m, 1H), 1.88 (m, 1H), 1.84 (m, 1H), 1.08 (d, J = 7.1 Hz , 3H), 1.05 (m, 21H), 1.02 (d, J = 6.9 Hz, 3H). 13C NMR (125 MHz, CDCl3) δ 77.7, 71.4, 65.2, 52.4, 42.6, 33.9, 31.5, 30.8, 26.5, 17.9, 13.1, 11.9, 11.5. [α]20D= -12.9 (c = 1.0, CHCl3). Anal. Calcd. for C20H42O3S2Si: C, 56.82 %, H, 10.01 %; Found: C, 56.53 %, H, 9.78 %.
(9:1 hexane/Et2O), yielding 0.649 g (66%) of the dithiane product as a white solid, m.p.: 367-369 K. Colourless crystals, suitable for X-ray diffraction, were obtained by slow diffusion of diethylether into a solution in hexanes at room temperature over a period of 2 days. 1H NMR (500 MHz, CDCl3)All atoms, except hydrogen, were refined anisotropically. The H atoms were placed at calculated positions using suitable riding models except those located on the hydroxy groups, which were found directly on the difference Fourier map and refined using DFIX constraints. Aliphatic H atoms were included in geometrically calculated positions, with C—H distances constrained to 0.98–1.00 Å. Methyl H atoms displacement parameters were set at Uiso(H) = 1.5Ueq(C). Hydroxy H atoms were located from a difference Fourier map and allowed to refine freely.
Data collection: APEX2 (Bruker, 2012); cell
SAINT (Bruker, 2012); data reduction: SAINT (Bruker, 2012); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2008); molecular graphics: Mercury (Macrae et al., 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).A view of the molecular structure of the two independent molecules (A and B) of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 50% probability level. A view along the c axis of the crystal packing of the title compound. The intermolecular hydrogen bonds are shown as dashed lines (see Table 1 for details; H atoms not involved in these interactions have been omitted for clarity). Reaction scheme. |
C20H42O3S2Si | F(000) = 928 |
Mr = 422.74 | Dx = 1.124 Mg m−3 |
Monoclinic, P21 | Cu Kα radiation, λ = 1.54178 Å |
a = 15.9691 (4) Å | Cell parameters from 8415 reflections |
b = 8.3420 (2) Å | θ = 2.8–70.9° |
c = 19.1245 (5) Å | µ = 2.51 mm−1 |
β = 101.253 (2)° | T = 124 K |
V = 2498.68 (11) Å3 | Block, colourless |
Z = 4 | 0.10 × 0.05 × 0.05 mm |
Bruker APEXII CCD diffractometer | 9653 independent reflections |
Radiation source: sealed tube | 8808 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.062 |
ϕ and ω scans | θmax = 71.8°, θmin = 2.4° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −19→19 |
Tmin = 0.860, Tmax = 0.882 | k = −10→10 |
38635 measured reflections | l = −23→23 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: mixed |
R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.088 | w = 1/[σ2(Fo2) + (0.0453P)2] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max = 0.001 |
9653 reflections | Δρmax = 0.41 e Å−3 |
501 parameters | Δρmin = −0.18 e Å−3 |
1 restraint | Absolute structure: Flack x determined using 3771 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
Primary atom site location: structure-invariant direct methods | Absolute structure parameter: 0.035 (8) |
C20H42O3S2Si | V = 2498.68 (11) Å3 |
Mr = 422.74 | Z = 4 |
Monoclinic, P21 | Cu Kα radiation |
a = 15.9691 (4) Å | µ = 2.51 mm−1 |
b = 8.3420 (2) Å | T = 124 K |
c = 19.1245 (5) Å | 0.10 × 0.05 × 0.05 mm |
β = 101.253 (2)° |
Bruker APEXII CCD diffractometer | 9653 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 8808 reflections with I > 2σ(I) |
Tmin = 0.860, Tmax = 0.882 | Rint = 0.062 |
38635 measured reflections |
R[F2 > 2σ(F2)] = 0.036 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.088 | Δρmax = 0.41 e Å−3 |
S = 1.02 | Δρmin = −0.18 e Å−3 |
9653 reflections | Absolute structure: Flack x determined using 3771 quotients [(I+)-(I-)]/[(I+)+(I-)] (Parsons et al., 2013) |
501 parameters | Absolute structure parameter: 0.035 (8) |
1 restraint |
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 | ||
S1 | 0.16186 (6) | 0.07437 (9) | 0.13813 (4) | 0.03371 (19) | |
S2 | 0.12503 (5) | 0.30070 (9) | 0.01309 (4) | 0.02892 (17) | |
Si1 | 0.34129 (5) | 0.86798 (10) | 0.37531 (4) | 0.02346 (17) | |
O1 | 0.26097 (14) | 0.7796 (3) | 0.32190 (13) | 0.0346 (5) | |
O2 | 0.04565 (13) | 0.7418 (3) | 0.22348 (11) | 0.0246 (4) | |
O3 | 0.01352 (14) | 0.4290 (3) | 0.19173 (11) | 0.0231 (4) | |
C1 | 0.11141 (19) | 0.2611 (4) | 0.10346 (14) | 0.0228 (6) | |
H1 | 0.0488 | 0.2513 | 0.1026 | 0.027* | |
C2 | 0.0977 (2) | −0.0623 (4) | 0.07562 (17) | 0.0341 (7) | |
H2A | 0.1158 | −0.1736 | 0.0886 | 0.041* | |
H2B | 0.0372 | −0.0516 | 0.0799 | 0.041* | |
C3 | 0.1048 (2) | −0.0325 (4) | −0.00130 (16) | 0.0312 (7) | |
H3A | 0.1658 | −0.0371 | −0.0050 | 0.037* | |
H3B | 0.0746 | −0.1193 | −0.0314 | 0.037* | |
C4 | 0.0684 (2) | 0.1269 (4) | −0.02988 (16) | 0.0326 (7) | |
H4A | 0.0081 | 0.1329 | −0.0243 | 0.039* | |
H4B | 0.0688 | 0.1317 | −0.0815 | 0.039* | |
C5 | 0.14528 (18) | 0.4037 (3) | 0.15198 (14) | 0.0205 (6) | |
H5 | 0.1256 | 0.5039 | 0.1250 | 0.025* | |
C6 | 0.24314 (19) | 0.4086 (4) | 0.16968 (16) | 0.0284 (6) | |
H6A | 0.2620 | 0.5113 | 0.1922 | 0.043* | |
H6B | 0.2654 | 0.3968 | 0.1257 | 0.043* | |
H6C | 0.2645 | 0.3208 | 0.2024 | 0.043* | |
C7 | 0.10345 (17) | 0.3999 (3) | 0.21755 (14) | 0.0200 (6) | |
H7 | 0.1103 | 0.2897 | 0.2385 | 0.024* | |
C8 | 0.13915 (17) | 0.5211 (3) | 0.27627 (13) | 0.0188 (5) | |
H8 | 0.2010 | 0.4961 | 0.2932 | 0.023* | |
C9 | 0.0945 (2) | 0.4992 (4) | 0.33964 (15) | 0.0267 (6) | |
H9A | 0.0348 | 0.5332 | 0.3260 | 0.040* | |
H9B | 0.1234 | 0.5642 | 0.3798 | 0.040* | |
H9C | 0.0967 | 0.3860 | 0.3536 | 0.040* | |
C10 | 0.13291 (17) | 0.6938 (3) | 0.24864 (14) | 0.0189 (5) | |
H10 | 0.1632 | 0.6998 | 0.2076 | 0.023* | |
C11 | 0.17329 (18) | 0.8160 (3) | 0.30402 (15) | 0.0229 (6) | |
H11A | 0.1648 | 0.9258 | 0.2843 | 0.028* | |
H11B | 0.1471 | 0.8092 | 0.3468 | 0.028* | |
C12 | 0.4239 (2) | 0.8970 (4) | 0.31910 (18) | 0.0331 (7) | |
H12 | 0.4404 | 0.7863 | 0.3070 | 0.040* | |
C13 | 0.5064 (2) | 0.9745 (6) | 0.3577 (2) | 0.0504 (10) | |
H13A | 0.5476 | 0.9778 | 0.3258 | 0.076* | |
H13B | 0.5301 | 0.9117 | 0.4002 | 0.076* | |
H13C | 0.4945 | 1.0839 | 0.3717 | 0.076* | |
C14 | 0.3906 (3) | 0.9783 (6) | 0.2472 (2) | 0.0548 (11) | |
H14A | 0.3811 | 1.0925 | 0.2548 | 0.082* | |
H14B | 0.3366 | 0.9283 | 0.2243 | 0.082* | |
H14C | 0.4326 | 0.9661 | 0.2165 | 0.082* | |
C15 | 0.3824 (2) | 0.7206 (4) | 0.44862 (19) | 0.0364 (8) | |
H15 | 0.4322 | 0.7713 | 0.4808 | 0.044* | |
C16 | 0.4144 (3) | 0.5676 (5) | 0.4182 (3) | 0.0536 (11) | |
H16A | 0.4326 | 0.4904 | 0.4568 | 0.080* | |
H16B | 0.4627 | 0.5935 | 0.3956 | 0.080* | |
H16C | 0.3682 | 0.5209 | 0.3827 | 0.080* | |
C17 | 0.3148 (3) | 0.6832 (6) | 0.4934 (3) | 0.0612 (14) | |
H17A | 0.2650 | 0.6338 | 0.4631 | 0.092* | |
H17B | 0.2976 | 0.7828 | 0.5139 | 0.092* | |
H17C | 0.3389 | 0.6092 | 0.5320 | 0.092* | |
C18 | 0.30313 (19) | 1.0552 (4) | 0.41417 (16) | 0.0265 (6) | |
H18 | 0.2490 | 1.0257 | 0.4298 | 0.032* | |
C19 | 0.3641 (2) | 1.1173 (5) | 0.48091 (19) | 0.0394 (8) | |
H19A | 0.4177 | 1.1520 | 0.4680 | 0.059* | |
H19B | 0.3758 | 1.0315 | 0.5164 | 0.059* | |
H19C | 0.3377 | 1.2082 | 0.5009 | 0.059* | |
C20 | 0.2804 (2) | 1.1928 (4) | 0.36050 (19) | 0.0357 (8) | |
H20A | 0.2537 | 1.2801 | 0.3826 | 0.054* | |
H20B | 0.2406 | 1.1539 | 0.3183 | 0.054* | |
H20C | 0.3325 | 1.2323 | 0.3464 | 0.054* | |
S3 | 0.86997 (5) | −0.22386 (9) | 0.49223 (4) | 0.02930 (18) | |
S4 | 0.83329 (5) | −0.44672 (9) | 0.36602 (4) | 0.03153 (18) | |
Si2 | 0.62445 (5) | 0.36336 (10) | 0.15228 (4) | 0.02448 (17) | |
O4 | 0.70944 (13) | 0.2498 (3) | 0.17766 (11) | 0.0284 (5) | |
O5 | 0.92962 (13) | 0.2292 (3) | 0.26956 (12) | 0.0265 (4) | |
O6 | 0.96444 (13) | −0.0785 (3) | 0.30587 (11) | 0.0236 (4) | |
C21 | 0.87904 (18) | −0.2564 (3) | 0.40019 (14) | 0.0214 (6) | |
H21 | 0.9412 | −0.2589 | 0.3985 | 0.026* | |
C22 | 0.9035 (2) | −0.5798 (4) | 0.42560 (16) | 0.0311 (7) | |
H22A | 0.8880 | −0.6921 | 0.4121 | 0.037* | |
H22B | 0.9629 | −0.5623 | 0.4194 | 0.037* | |
C23 | 0.8996 (2) | −0.5564 (4) | 0.50376 (16) | 0.0281 (6) | |
H23A | 0.9340 | −0.6412 | 0.5322 | 0.034* | |
H23B | 0.8398 | −0.5690 | 0.5097 | 0.034* | |
C24 | 0.9324 (2) | −0.3933 (4) | 0.53254 (16) | 0.0325 (7) | |
H24A | 0.9918 | −0.3803 | 0.5253 | 0.039* | |
H24B | 0.9340 | −0.3912 | 0.5845 | 0.039* | |
C25 | 0.83857 (17) | −0.1149 (3) | 0.35346 (14) | 0.0210 (6) | |
H25 | 0.8580 | −0.0140 | 0.3799 | 0.025* | |
C26 | 0.74090 (18) | −0.1173 (4) | 0.34094 (16) | 0.0286 (6) | |
H26A | 0.7185 | −0.0135 | 0.3218 | 0.043* | |
H26B | 0.7227 | −0.1377 | 0.3862 | 0.043* | |
H26C | 0.7190 | −0.2022 | 0.3068 | 0.043* | |
C27 | 0.87422 (17) | −0.1132 (3) | 0.28443 (14) | 0.0208 (6) | |
H27 | 0.8682 | −0.2235 | 0.2636 | 0.025* | |
C28 | 0.83230 (18) | 0.0047 (3) | 0.22688 (14) | 0.0203 (5) | |
H28 | 0.7698 | −0.0201 | 0.2160 | 0.024* | |
C29 | 0.8661 (2) | −0.0222 (4) | 0.15776 (15) | 0.0312 (7) | |
H29A | 0.9259 | 0.0117 | 0.1649 | 0.047* | |
H29B | 0.8320 | 0.0407 | 0.1191 | 0.047* | |
H29C | 0.8619 | −0.1362 | 0.1452 | 0.047* | |
C30 | 0.84170 (17) | 0.1791 (3) | 0.25221 (14) | 0.0198 (5) | |
H30 | 0.8171 | 0.1882 | 0.2963 | 0.024* | |
C31 | 0.79599 (18) | 0.2985 (4) | 0.19808 (15) | 0.0234 (6) | |
H31A | 0.7991 | 0.4072 | 0.2193 | 0.028* | |
H31B | 0.8233 | 0.3015 | 0.1559 | 0.028* | |
C32 | 0.6343 (2) | 0.4814 (4) | 0.07042 (18) | 0.0355 (7) | |
H32 | 0.5776 | 0.5324 | 0.0519 | 0.043* | |
C33 | 0.6545 (2) | 0.3703 (6) | 0.01114 (17) | 0.0457 (9) | |
H33A | 0.6638 | 0.4353 | −0.0294 | 0.069* | |
H33B | 0.6065 | 0.2972 | −0.0045 | 0.069* | |
H33C | 0.7061 | 0.3080 | 0.0297 | 0.069* | |
C34 | 0.7010 (2) | 0.6176 (5) | 0.0870 (2) | 0.0431 (9) | |
H34A | 0.7575 | 0.5714 | 0.1051 | 0.065* | |
H34B | 0.6854 | 0.6893 | 0.1230 | 0.065* | |
H34C | 0.7022 | 0.6783 | 0.0433 | 0.065* | |
C35 | 0.5335 (2) | 0.2169 (4) | 0.13596 (18) | 0.0343 (7) | |
H35 | 0.5193 | 0.1932 | 0.1836 | 0.041* | |
C36 | 0.5558 (2) | 0.0553 (5) | 0.1054 (2) | 0.0487 (10) | |
H36A | 0.5071 | −0.0178 | 0.1017 | 0.073* | |
H36B | 0.6055 | 0.0086 | 0.1371 | 0.073* | |
H36C | 0.5690 | 0.0721 | 0.0580 | 0.073* | |
C37 | 0.4521 (2) | 0.2851 (5) | 0.0896 (2) | 0.0523 (11) | |
H37A | 0.4609 | 0.2991 | 0.0406 | 0.078* | |
H37B | 0.4388 | 0.3890 | 0.1087 | 0.078* | |
H37C | 0.4046 | 0.2109 | 0.0897 | 0.078* | |
C38 | 0.6164 (2) | 0.5038 (5) | 0.2277 (2) | 0.0392 (8) | |
H38 | 0.6716 | 0.5636 | 0.2388 | 0.047* | |
C39 | 0.5455 (3) | 0.6314 (6) | 0.2079 (3) | 0.0607 (12) | |
H39A | 0.4894 | 0.5796 | 0.2019 | 0.091* | |
H39B | 0.5512 | 0.6840 | 0.1633 | 0.091* | |
H39C | 0.5508 | 0.7115 | 0.2461 | 0.091* | |
C40 | 0.6076 (3) | 0.4152 (6) | 0.2961 (2) | 0.0589 (12) | |
H40A | 0.6094 | 0.4927 | 0.3349 | 0.088* | |
H40B | 0.6547 | 0.3387 | 0.3089 | 0.088* | |
H40C | 0.5531 | 0.3574 | 0.2883 | 0.088* | |
H101 | −0.007 (2) | 0.392 (5) | 0.2137 (18) | 0.018 (10)* | |
H102 | 0.988 (2) | −0.124 (5) | 0.2815 (19) | 0.030 (10)* | |
H100 | 0.022 (3) | 0.665 (5) | 0.210 (2) | 0.028 (10)* | |
H103 | 0.955 (3) | 0.150 (6) | 0.286 (2) | 0.041 (12)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0478 (5) | 0.0229 (4) | 0.0248 (4) | 0.0026 (3) | −0.0070 (3) | 0.0004 (3) |
S2 | 0.0402 (4) | 0.0279 (4) | 0.0189 (3) | −0.0032 (3) | 0.0062 (3) | 0.0004 (3) |
Si1 | 0.0160 (3) | 0.0193 (4) | 0.0325 (4) | −0.0007 (3) | −0.0017 (3) | 0.0017 (3) |
O1 | 0.0169 (10) | 0.0278 (12) | 0.0539 (14) | 0.0016 (9) | −0.0058 (9) | −0.0108 (10) |
O2 | 0.0193 (10) | 0.0245 (11) | 0.0268 (10) | 0.0047 (9) | −0.0032 (8) | −0.0011 (9) |
O3 | 0.0185 (10) | 0.0284 (11) | 0.0216 (10) | −0.0023 (9) | 0.0020 (8) | 0.0012 (9) |
C1 | 0.0259 (15) | 0.0237 (15) | 0.0185 (13) | −0.0004 (11) | 0.0034 (10) | 0.0011 (11) |
C2 | 0.048 (2) | 0.0244 (16) | 0.0268 (16) | −0.0052 (14) | −0.0002 (13) | −0.0017 (12) |
C3 | 0.0356 (18) | 0.0297 (17) | 0.0274 (15) | −0.0036 (14) | 0.0041 (12) | −0.0068 (13) |
C4 | 0.0422 (19) | 0.0329 (17) | 0.0201 (14) | −0.0031 (14) | −0.0001 (12) | −0.0044 (13) |
C5 | 0.0207 (14) | 0.0191 (14) | 0.0207 (12) | −0.0003 (10) | 0.0018 (10) | 0.0008 (10) |
C6 | 0.0217 (15) | 0.0313 (16) | 0.0324 (15) | −0.0026 (12) | 0.0055 (11) | −0.0052 (12) |
C7 | 0.0180 (13) | 0.0208 (14) | 0.0195 (13) | −0.0003 (10) | −0.0005 (9) | 0.0018 (10) |
C8 | 0.0183 (13) | 0.0197 (13) | 0.0173 (12) | 0.0004 (10) | 0.0007 (10) | 0.0019 (10) |
C9 | 0.0306 (16) | 0.0290 (16) | 0.0199 (13) | −0.0049 (13) | 0.0037 (11) | 0.0011 (12) |
C10 | 0.0166 (13) | 0.0201 (13) | 0.0185 (12) | 0.0023 (10) | 0.0000 (9) | 0.0030 (10) |
C11 | 0.0174 (13) | 0.0221 (14) | 0.0278 (14) | 0.0013 (10) | 0.0006 (10) | −0.0006 (11) |
C12 | 0.0240 (15) | 0.0360 (19) | 0.0398 (17) | 0.0020 (13) | 0.0077 (12) | −0.0019 (14) |
C13 | 0.0262 (19) | 0.064 (3) | 0.064 (2) | −0.0159 (18) | 0.0150 (17) | −0.010 (2) |
C14 | 0.045 (2) | 0.079 (3) | 0.044 (2) | 0.008 (2) | 0.0183 (17) | 0.018 (2) |
C15 | 0.0236 (15) | 0.0299 (17) | 0.050 (2) | 0.0006 (13) | −0.0059 (14) | 0.0114 (15) |
C16 | 0.044 (2) | 0.0252 (18) | 0.080 (3) | 0.0043 (16) | −0.017 (2) | 0.0063 (19) |
C17 | 0.039 (2) | 0.067 (3) | 0.073 (3) | 0.002 (2) | 0.000 (2) | 0.049 (2) |
C18 | 0.0237 (14) | 0.0247 (15) | 0.0298 (15) | 0.0001 (12) | 0.0020 (11) | 0.0003 (12) |
C19 | 0.038 (2) | 0.039 (2) | 0.0381 (19) | 0.0020 (16) | −0.0016 (14) | −0.0084 (15) |
C20 | 0.0358 (18) | 0.0216 (15) | 0.0456 (19) | 0.0034 (13) | −0.0023 (14) | 0.0001 (14) |
S3 | 0.0408 (4) | 0.0261 (4) | 0.0210 (3) | 0.0026 (3) | 0.0060 (3) | −0.0025 (3) |
S4 | 0.0409 (4) | 0.0210 (4) | 0.0263 (4) | 0.0013 (3) | −0.0093 (3) | −0.0033 (3) |
Si2 | 0.0200 (4) | 0.0211 (4) | 0.0301 (4) | 0.0008 (3) | −0.0004 (3) | 0.0005 (3) |
O4 | 0.0210 (10) | 0.0232 (10) | 0.0368 (11) | 0.0011 (8) | −0.0046 (8) | 0.0013 (9) |
O5 | 0.0189 (10) | 0.0244 (11) | 0.0334 (11) | −0.0024 (9) | −0.0013 (8) | 0.0020 (9) |
O6 | 0.0175 (10) | 0.0281 (11) | 0.0238 (10) | 0.0033 (8) | 0.0006 (8) | −0.0012 (8) |
C21 | 0.0246 (14) | 0.0219 (14) | 0.0169 (12) | 0.0000 (11) | 0.0025 (10) | −0.0034 (11) |
C22 | 0.0375 (18) | 0.0256 (15) | 0.0280 (15) | 0.0084 (13) | 0.0012 (12) | 0.0022 (12) |
C23 | 0.0294 (16) | 0.0298 (16) | 0.0257 (15) | 0.0018 (13) | 0.0072 (12) | 0.0044 (12) |
C24 | 0.0434 (19) | 0.0316 (17) | 0.0198 (14) | 0.0005 (14) | −0.0011 (12) | 0.0033 (12) |
C25 | 0.0205 (13) | 0.0197 (14) | 0.0214 (13) | 0.0010 (11) | 0.0006 (10) | −0.0015 (11) |
C26 | 0.0220 (14) | 0.0311 (16) | 0.0330 (15) | 0.0054 (13) | 0.0063 (11) | 0.0031 (13) |
C27 | 0.0190 (13) | 0.0203 (14) | 0.0211 (13) | 0.0006 (11) | −0.0008 (10) | −0.0046 (11) |
C28 | 0.0203 (13) | 0.0209 (14) | 0.0187 (12) | 0.0029 (11) | 0.0010 (10) | −0.0021 (10) |
C29 | 0.0395 (18) | 0.0332 (17) | 0.0199 (14) | 0.0095 (14) | 0.0030 (12) | −0.0034 (12) |
C30 | 0.0175 (14) | 0.0199 (14) | 0.0209 (13) | 0.0004 (10) | 0.0014 (10) | −0.0021 (10) |
C31 | 0.0205 (14) | 0.0220 (13) | 0.0259 (13) | −0.0005 (11) | −0.0001 (10) | 0.0005 (11) |
C32 | 0.0297 (17) | 0.0385 (19) | 0.0366 (17) | 0.0037 (14) | 0.0025 (13) | 0.0103 (15) |
C33 | 0.042 (2) | 0.064 (3) | 0.0306 (16) | −0.001 (2) | 0.0052 (13) | 0.0022 (18) |
C34 | 0.036 (2) | 0.038 (2) | 0.055 (2) | −0.0006 (16) | 0.0095 (16) | 0.0163 (17) |
C35 | 0.0280 (16) | 0.0317 (17) | 0.0405 (18) | −0.0092 (14) | 0.0005 (13) | −0.0033 (14) |
C36 | 0.037 (2) | 0.0311 (19) | 0.070 (3) | −0.0056 (16) | −0.0091 (18) | −0.0081 (18) |
C37 | 0.0233 (18) | 0.047 (2) | 0.080 (3) | −0.0008 (16) | −0.0066 (17) | −0.010 (2) |
C38 | 0.0318 (18) | 0.039 (2) | 0.047 (2) | −0.0044 (15) | 0.0089 (14) | −0.0155 (16) |
C39 | 0.048 (3) | 0.050 (3) | 0.087 (3) | 0.008 (2) | 0.019 (2) | −0.025 (2) |
C40 | 0.058 (3) | 0.081 (3) | 0.040 (2) | −0.018 (2) | 0.0149 (18) | −0.019 (2) |
S1—C2 | 1.816 (3) | S3—C24 | 1.813 (3) |
S1—C1 | 1.819 (3) | S3—C21 | 1.814 (3) |
S2—C1 | 1.814 (3) | S4—C22 | 1.813 (3) |
S2—C4 | 1.818 (3) | S4—C21 | 1.815 (3) |
Si1—O1 | 1.649 (2) | Si2—O4 | 1.649 (2) |
Si1—C12 | 1.873 (3) | Si2—C35 | 1.877 (3) |
Si1—C18 | 1.882 (3) | Si2—C32 | 1.882 (3) |
Si1—C15 | 1.884 (3) | Si2—C38 | 1.883 (4) |
O1—C11 | 1.408 (3) | O4—C31 | 1.420 (3) |
O2—C10 | 1.439 (3) | O5—C30 | 1.440 (3) |
O2—H100 | 0.76 (4) | O5—H103 | 0.80 (5) |
O3—C7 | 1.445 (3) | O6—C27 | 1.448 (3) |
O3—H101 | 0.66 (4) | O6—H102 | 0.76 (4) |
C1—C5 | 1.540 (4) | C21—C25 | 1.544 (4) |
C1—H1 | 1.0000 | C21—H21 | 1.0000 |
C2—C3 | 1.518 (4) | C22—C23 | 1.520 (4) |
C2—H2A | 0.9900 | C22—H22A | 0.9900 |
C2—H2B | 0.9900 | C22—H22B | 0.9900 |
C3—C4 | 1.511 (5) | C23—C24 | 1.523 (5) |
C3—H3A | 0.9900 | C23—H23A | 0.9900 |
C3—H3B | 0.9900 | C23—H23B | 0.9900 |
C4—H4A | 0.9900 | C24—H24A | 0.9900 |
C4—H4B | 0.9900 | C24—H24B | 0.9900 |
C5—C7 | 1.532 (4) | C25—C26 | 1.531 (4) |
C5—C6 | 1.533 (4) | C25—C27 | 1.537 (4) |
C5—H5 | 1.0000 | C25—H25 | 1.0000 |
C6—H6A | 0.9800 | C26—H26A | 0.9800 |
C6—H6B | 0.9800 | C26—H26B | 0.9800 |
C6—H6C | 0.9800 | C26—H26C | 0.9800 |
C7—C8 | 1.536 (4) | C27—C28 | 1.529 (4) |
C7—H7 | 1.0000 | C27—H27 | 1.0000 |
C8—C10 | 1.531 (4) | C28—C30 | 1.531 (4) |
C8—C9 | 1.533 (4) | C28—C29 | 1.539 (4) |
C8—H8 | 1.0000 | C28—H28 | 1.0000 |
C9—H9A | 0.9800 | C29—H29A | 0.9800 |
C9—H9B | 0.9800 | C29—H29B | 0.9800 |
C9—H9C | 0.9800 | C29—H29C | 0.9800 |
C10—C11 | 1.520 (4) | C30—C31 | 1.518 (4) |
C10—H10 | 1.0000 | C30—H30 | 1.0000 |
C11—H11A | 0.9900 | C31—H31A | 0.9900 |
C11—H11B | 0.9900 | C31—H31B | 0.9900 |
C12—C13 | 1.522 (5) | C32—C33 | 1.547 (5) |
C12—C14 | 1.533 (5) | C32—C34 | 1.547 (5) |
C12—H12 | 1.0000 | C32—H32 | 1.0000 |
C13—H13A | 0.9800 | C33—H33A | 0.9800 |
C13—H13B | 0.9800 | C33—H33B | 0.9800 |
C13—H13C | 0.9800 | C33—H33C | 0.9800 |
C14—H14A | 0.9800 | C34—H34A | 0.9800 |
C14—H14B | 0.9800 | C34—H34B | 0.9800 |
C14—H14C | 0.9800 | C34—H34C | 0.9800 |
C15—C16 | 1.531 (5) | C35—C37 | 1.533 (5) |
C15—C17 | 1.536 (6) | C35—C36 | 1.538 (5) |
C15—H15 | 1.0000 | C35—H35 | 1.0000 |
C16—H16A | 0.9800 | C36—H36A | 0.9800 |
C16—H16B | 0.9800 | C36—H36B | 0.9800 |
C16—H16C | 0.9800 | C36—H36C | 0.9800 |
C17—H17A | 0.9800 | C37—H37A | 0.9800 |
C17—H17B | 0.9800 | C37—H37B | 0.9800 |
C17—H17C | 0.9800 | C37—H37C | 0.9800 |
C18—C20 | 1.535 (4) | C38—C40 | 1.533 (6) |
C18—C19 | 1.536 (4) | C38—C39 | 1.546 (6) |
C18—H18 | 1.0000 | C38—H38 | 1.0000 |
C19—H19A | 0.9800 | C39—H39A | 0.9800 |
C19—H19B | 0.9800 | C39—H39B | 0.9800 |
C19—H19C | 0.9800 | C39—H39C | 0.9800 |
C20—H20A | 0.9800 | C40—H40A | 0.9800 |
C20—H20B | 0.9800 | C40—H40B | 0.9800 |
C20—H20C | 0.9800 | C40—H40C | 0.9800 |
C2—S1—C1 | 98.33 (15) | C24—S3—C21 | 98.88 (14) |
C1—S2—C4 | 98.28 (14) | C22—S4—C21 | 98.81 (14) |
O1—Si1—C12 | 104.60 (14) | O4—Si2—C35 | 103.93 (14) |
O1—Si1—C18 | 110.06 (13) | O4—Si2—C32 | 110.38 (14) |
C12—Si1—C18 | 115.97 (15) | C35—Si2—C32 | 112.94 (16) |
O1—Si1—C15 | 106.58 (14) | O4—Si2—C38 | 107.91 (14) |
C12—Si1—C15 | 109.22 (15) | C35—Si2—C38 | 111.46 (16) |
C18—Si1—C15 | 109.91 (15) | C32—Si2—C38 | 109.95 (17) |
C11—O1—Si1 | 132.1 (2) | C31—O4—Si2 | 128.14 (19) |
C10—O2—H100 | 105 (3) | C30—O5—H103 | 104 (3) |
C7—O3—H101 | 107 (3) | C27—O6—H102 | 108 (3) |
C5—C1—S2 | 109.89 (19) | C25—C21—S3 | 110.08 (19) |
C5—C1—S1 | 111.31 (19) | C25—C21—S4 | 111.50 (18) |
S2—C1—S1 | 112.11 (16) | S3—C21—S4 | 112.18 (16) |
C5—C1—H1 | 107.8 | C25—C21—H21 | 107.6 |
S2—C1—H1 | 107.8 | S3—C21—H21 | 107.6 |
S1—C1—H1 | 107.8 | S4—C21—H21 | 107.6 |
C3—C2—S1 | 113.3 (2) | C23—C22—S4 | 113.6 (2) |
C3—C2—H2A | 108.9 | C23—C22—H22A | 108.8 |
S1—C2—H2A | 108.9 | S4—C22—H22A | 108.8 |
C3—C2—H2B | 108.9 | C23—C22—H22B | 108.8 |
S1—C2—H2B | 108.9 | S4—C22—H22B | 108.8 |
H2A—C2—H2B | 107.7 | H22A—C22—H22B | 107.7 |
C4—C3—C2 | 113.5 (3) | C22—C23—C24 | 113.1 (3) |
C4—C3—H3A | 108.9 | C22—C23—H23A | 109.0 |
C2—C3—H3A | 108.9 | C24—C23—H23A | 109.0 |
C4—C3—H3B | 108.9 | C22—C23—H23B | 109.0 |
C2—C3—H3B | 108.9 | C24—C23—H23B | 109.0 |
H3A—C3—H3B | 107.7 | H23A—C23—H23B | 107.8 |
C3—C4—S2 | 114.5 (2) | C23—C24—S3 | 114.9 (2) |
C3—C4—H4A | 108.6 | C23—C24—H24A | 108.5 |
S2—C4—H4A | 108.6 | S3—C24—H24A | 108.5 |
C3—C4—H4B | 108.6 | C23—C24—H24B | 108.5 |
S2—C4—H4B | 108.6 | S3—C24—H24B | 108.5 |
H4A—C4—H4B | 107.6 | H24A—C24—H24B | 107.5 |
C7—C5—C6 | 114.1 (2) | C26—C25—C27 | 113.7 (2) |
C7—C5—C1 | 108.6 (2) | C26—C25—C21 | 112.3 (2) |
C6—C5—C1 | 112.1 (2) | C27—C25—C21 | 108.7 (2) |
C7—C5—H5 | 107.2 | C26—C25—H25 | 107.2 |
C6—C5—H5 | 107.2 | C27—C25—H25 | 107.2 |
C1—C5—H5 | 107.2 | C21—C25—H25 | 107.2 |
C5—C6—H6A | 109.5 | C25—C26—H26A | 109.5 |
C5—C6—H6B | 109.5 | C25—C26—H26B | 109.5 |
H6A—C6—H6B | 109.5 | H26A—C26—H26B | 109.5 |
C5—C6—H6C | 109.5 | C25—C26—H26C | 109.5 |
H6A—C6—H6C | 109.5 | H26A—C26—H26C | 109.5 |
H6B—C6—H6C | 109.5 | H26B—C26—H26C | 109.5 |
O3—C7—C5 | 106.2 (2) | O6—C27—C28 | 110.3 (2) |
O3—C7—C8 | 110.0 (2) | O6—C27—C25 | 105.9 (2) |
C5—C7—C8 | 115.2 (2) | C28—C27—C25 | 116.2 (2) |
O3—C7—H7 | 108.4 | O6—C27—H27 | 108.1 |
C5—C7—H7 | 108.4 | C28—C27—H27 | 108.1 |
C8—C7—H7 | 108.4 | C25—C27—H27 | 108.1 |
C10—C8—C9 | 112.1 (2) | C27—C28—C30 | 112.4 (2) |
C10—C8—C7 | 112.2 (2) | C27—C28—C29 | 110.3 (2) |
C9—C8—C7 | 109.6 (2) | C30—C28—C29 | 112.4 (2) |
C10—C8—H8 | 107.6 | C27—C28—H28 | 107.1 |
C9—C8—H8 | 107.6 | C30—C28—H28 | 107.1 |
C7—C8—H8 | 107.6 | C29—C28—H28 | 107.1 |
C8—C9—H9A | 109.5 | C28—C29—H29A | 109.5 |
C8—C9—H9B | 109.5 | C28—C29—H29B | 109.5 |
H9A—C9—H9B | 109.5 | H29A—C29—H29B | 109.5 |
C8—C9—H9C | 109.5 | C28—C29—H29C | 109.5 |
H9A—C9—H9C | 109.5 | H29A—C29—H29C | 109.5 |
H9B—C9—H9C | 109.5 | H29B—C29—H29C | 109.5 |
O2—C10—C11 | 107.3 (2) | O5—C30—C31 | 106.5 (2) |
O2—C10—C8 | 111.7 (2) | O5—C30—C28 | 112.3 (2) |
C11—C10—C8 | 113.6 (2) | C31—C30—C28 | 113.8 (2) |
O2—C10—H10 | 108.0 | O5—C30—H30 | 108.0 |
C11—C10—H10 | 108.0 | C31—C30—H30 | 108.0 |
C8—C10—H10 | 108.0 | C28—C30—H30 | 108.0 |
O1—C11—C10 | 106.9 (2) | O4—C31—C30 | 108.2 (2) |
O1—C11—H11A | 110.3 | O4—C31—H31A | 110.1 |
C10—C11—H11A | 110.3 | C30—C31—H31A | 110.1 |
O1—C11—H11B | 110.3 | O4—C31—H31B | 110.1 |
C10—C11—H11B | 110.3 | C30—C31—H31B | 110.1 |
H11A—C11—H11B | 108.6 | H31A—C31—H31B | 108.4 |
C13—C12—C14 | 111.3 (3) | C33—C32—C34 | 110.8 (3) |
C13—C12—Si1 | 114.6 (2) | C33—C32—Si2 | 111.1 (3) |
C14—C12—Si1 | 114.3 (2) | C34—C32—Si2 | 112.3 (2) |
C13—C12—H12 | 105.2 | C33—C32—H32 | 107.4 |
C14—C12—H12 | 105.2 | C34—C32—H32 | 107.4 |
Si1—C12—H12 | 105.2 | Si2—C32—H32 | 107.4 |
C12—C13—H13A | 109.5 | C32—C33—H33A | 109.5 |
C12—C13—H13B | 109.5 | C32—C33—H33B | 109.5 |
H13A—C13—H13B | 109.5 | H33A—C33—H33B | 109.5 |
C12—C13—H13C | 109.5 | C32—C33—H33C | 109.5 |
H13A—C13—H13C | 109.5 | H33A—C33—H33C | 109.5 |
H13B—C13—H13C | 109.5 | H33B—C33—H33C | 109.5 |
C12—C14—H14A | 109.5 | C32—C34—H34A | 109.5 |
C12—C14—H14B | 109.5 | C32—C34—H34B | 109.5 |
H14A—C14—H14B | 109.5 | H34A—C34—H34B | 109.5 |
C12—C14—H14C | 109.5 | C32—C34—H34C | 109.5 |
H14A—C14—H14C | 109.5 | H34A—C34—H34C | 109.5 |
H14B—C14—H14C | 109.5 | H34B—C34—H34C | 109.5 |
C16—C15—C17 | 111.4 (3) | C37—C35—C36 | 109.8 (3) |
C16—C15—Si1 | 110.8 (3) | C37—C35—Si2 | 113.3 (3) |
C17—C15—Si1 | 111.5 (2) | C36—C35—Si2 | 113.9 (3) |
C16—C15—H15 | 107.6 | C37—C35—H35 | 106.4 |
C17—C15—H15 | 107.6 | C36—C35—H35 | 106.4 |
Si1—C15—H15 | 107.6 | Si2—C35—H35 | 106.4 |
C15—C16—H16A | 109.5 | C35—C36—H36A | 109.5 |
C15—C16—H16B | 109.5 | C35—C36—H36B | 109.5 |
H16A—C16—H16B | 109.5 | H36A—C36—H36B | 109.5 |
C15—C16—H16C | 109.5 | C35—C36—H36C | 109.5 |
H16A—C16—H16C | 109.5 | H36A—C36—H36C | 109.5 |
H16B—C16—H16C | 109.5 | H36B—C36—H36C | 109.5 |
C15—C17—H17A | 109.5 | C35—C37—H37A | 109.5 |
C15—C17—H17B | 109.5 | C35—C37—H37B | 109.5 |
H17A—C17—H17B | 109.5 | H37A—C37—H37B | 109.5 |
C15—C17—H17C | 109.5 | C35—C37—H37C | 109.5 |
H17A—C17—H17C | 109.5 | H37A—C37—H37C | 109.5 |
H17B—C17—H17C | 109.5 | H37B—C37—H37C | 109.5 |
C20—C18—C19 | 109.4 (3) | C40—C38—C39 | 110.9 (4) |
C20—C18—Si1 | 114.1 (2) | C40—C38—Si2 | 112.7 (3) |
C19—C18—Si1 | 114.0 (2) | C39—C38—Si2 | 113.4 (3) |
C20—C18—H18 | 106.2 | C40—C38—H38 | 106.4 |
C19—C18—H18 | 106.2 | C39—C38—H38 | 106.4 |
Si1—C18—H18 | 106.2 | Si2—C38—H38 | 106.4 |
C18—C19—H19A | 109.5 | C38—C39—H39A | 109.5 |
C18—C19—H19B | 109.5 | C38—C39—H39B | 109.5 |
H19A—C19—H19B | 109.5 | H39A—C39—H39B | 109.5 |
C18—C19—H19C | 109.5 | C38—C39—H39C | 109.5 |
H19A—C19—H19C | 109.5 | H39A—C39—H39C | 109.5 |
H19B—C19—H19C | 109.5 | H39B—C39—H39C | 109.5 |
C18—C20—H20A | 109.5 | C38—C40—H40A | 109.5 |
C18—C20—H20B | 109.5 | C38—C40—H40B | 109.5 |
H20A—C20—H20B | 109.5 | H40A—C40—H40B | 109.5 |
C18—C20—H20C | 109.5 | C38—C40—H40C | 109.5 |
H20A—C20—H20C | 109.5 | H40A—C40—H40C | 109.5 |
H20B—C20—H20C | 109.5 | H40B—C40—H40C | 109.5 |
C12—Si1—O1—C11 | −128.0 (3) | C35—Si2—O4—C31 | −178.8 (2) |
C18—Si1—O1—C11 | −2.8 (3) | C32—Si2—O4—C31 | 59.8 (3) |
C15—Si1—O1—C11 | 116.4 (3) | C38—Si2—O4—C31 | −60.4 (3) |
C4—S2—C1—C5 | −173.4 (2) | C24—S3—C21—C25 | −173.8 (2) |
C4—S2—C1—S1 | 62.28 (19) | C24—S3—C21—S4 | 61.44 (19) |
C2—S1—C1—C5 | 173.0 (2) | C22—S4—C21—C25 | 173.3 (2) |
C2—S1—C1—S2 | −63.40 (19) | C22—S4—C21—S3 | −62.73 (19) |
C1—S1—C2—C3 | 61.1 (3) | C21—S4—C22—C23 | 61.1 (3) |
S1—C2—C3—C4 | −65.9 (4) | S4—C22—C23—C24 | −65.4 (3) |
C2—C3—C4—S2 | 65.3 (4) | C22—C23—C24—S3 | 64.5 (3) |
C1—S2—C4—C3 | −59.6 (3) | C21—S3—C24—C23 | −58.9 (3) |
S2—C1—C5—C7 | 158.25 (18) | S3—C21—C25—C26 | −73.4 (3) |
S1—C1—C5—C7 | −77.0 (2) | S4—C21—C25—C26 | 51.8 (3) |
S2—C1—C5—C6 | −74.8 (3) | S3—C21—C25—C27 | 159.84 (18) |
S1—C1—C5—C6 | 50.0 (3) | S4—C21—C25—C27 | −75.0 (2) |
C6—C5—C7—O3 | 168.4 (2) | C26—C25—C27—O6 | 168.7 (2) |
C1—C5—C7—O3 | −65.7 (3) | C21—C25—C27—O6 | −65.3 (3) |
C6—C5—C7—C8 | 46.4 (3) | C26—C25—C27—C28 | 45.9 (3) |
C1—C5—C7—C8 | 172.3 (2) | C21—C25—C27—C28 | 171.9 (2) |
O3—C7—C8—C10 | −62.8 (3) | O6—C27—C28—C30 | −59.3 (3) |
C5—C7—C8—C10 | 57.2 (3) | C25—C27—C28—C30 | 61.1 (3) |
O3—C7—C8—C9 | 62.5 (3) | O6—C27—C28—C29 | 67.0 (3) |
C5—C7—C8—C9 | −177.5 (2) | C25—C27—C28—C29 | −172.6 (2) |
C9—C8—C10—O2 | −61.4 (3) | C27—C28—C30—O5 | 62.6 (3) |
C7—C8—C10—O2 | 62.4 (3) | C29—C28—C30—O5 | −62.6 (3) |
C9—C8—C10—C11 | 60.2 (3) | C27—C28—C30—C31 | −176.3 (2) |
C7—C8—C10—C11 | −176.0 (2) | C29—C28—C30—C31 | 58.5 (3) |
Si1—O1—C11—C10 | 177.0 (2) | Si2—O4—C31—C30 | 149.5 (2) |
O2—C10—C11—O1 | −172.9 (2) | O5—C30—C31—O4 | 178.0 (2) |
C8—C10—C11—O1 | 63.0 (3) | C28—C30—C31—O4 | 53.7 (3) |
O1—Si1—C12—C13 | −178.7 (3) | O4—Si2—C32—C33 | 52.6 (3) |
C18—Si1—C12—C13 | 59.9 (3) | C35—Si2—C32—C33 | −63.3 (3) |
C15—Si1—C12—C13 | −64.9 (3) | C38—Si2—C32—C33 | 171.5 (2) |
O1—Si1—C12—C14 | 51.1 (3) | O4—Si2—C32—C34 | −72.2 (3) |
C18—Si1—C12—C14 | −70.3 (3) | C35—Si2—C32—C34 | 171.9 (3) |
C15—Si1—C12—C14 | 164.9 (3) | C38—Si2—C32—C34 | 46.7 (3) |
O1—Si1—C15—C16 | 61.1 (3) | O4—Si2—C35—C37 | −161.4 (3) |
C12—Si1—C15—C16 | −51.4 (3) | C32—Si2—C35—C37 | −41.7 (3) |
C18—Si1—C15—C16 | −179.6 (2) | C38—Si2—C35—C37 | 82.6 (3) |
O1—Si1—C15—C17 | −63.6 (3) | O4—Si2—C35—C36 | −35.0 (3) |
C12—Si1—C15—C17 | −176.1 (3) | C32—Si2—C35—C36 | 84.7 (3) |
C18—Si1—C15—C17 | 55.6 (3) | C38—Si2—C35—C36 | −150.9 (3) |
O1—Si1—C18—C20 | −71.4 (3) | O4—Si2—C38—C40 | −59.9 (3) |
C12—Si1—C18—C20 | 47.1 (3) | C35—Si2—C38—C40 | 53.6 (3) |
C15—Si1—C18—C20 | 171.5 (2) | C32—Si2—C38—C40 | 179.6 (3) |
O1—Si1—C18—C19 | 161.9 (2) | O4—Si2—C38—C39 | 173.1 (3) |
C12—Si1—C18—C19 | −79.6 (3) | C35—Si2—C38—C39 | −73.4 (3) |
C15—Si1—C18—C19 | 44.8 (3) | C32—Si2—C38—C39 | 52.6 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H100···O3 | 0.76 (4) | 2.00 (4) | 2.705 (4) | 154 (5) |
O5—H103···O6 | 0.81 (5) | 1.94 (5) | 2.689 (3) | 153 (5) |
O3—H101···O5i | 0.66 (3) | 2.11 (4) | 2.751 (3) | 167 (5) |
O6—H102···O2ii | 0.76 (4) | 1.93 (4) | 2.685 (3) | 175 (4) |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y−1, z. |
D—H···A | D—H | H···A | D···A | D—H···A |
O2—H100···O3 | 0.76 (4) | 2.00 (4) | 2.705 (4) | 154 (5) |
O5—H103···O6 | 0.81 (5) | 1.94 (5) | 2.689 (3) | 153 (5) |
O3—H101···O5i | 0.66 (3) | 2.11 (4) | 2.751 (3) | 167 (5) |
O6—H102···O2ii | 0.76 (4) | 1.93 (4) | 2.685 (3) | 175 (4) |
Symmetry codes: (i) x−1, y, z; (ii) x+1, y−1, z. |
Acknowledgements
The authors thank the American Crystallographic Association Summer School and the University of Notre Dame for the use of their X-ray diffraction facilities. We also thank NIH NIGMS RISE (5R25GM061151–12) and SCORE (5SC1GM084826–04) for financial support.
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The synthesis of the title compound was obtained through regioselective epoxide cleavage of (-)-(2R,3R)-3-((2R,3S)-3-methyloxiran-2-yl)-1- ((triisopropylsilyl)oxy)butan-2-ol with 1,3-dithiane in the presence of tert-butyllithium and di-n-butylmagnesium as metallation reagents. This reaction afforded the optically active syn,anti,anti-polypropionate unit needed for the synthesis of (+)-crocacin C with the correct 2R,3S,4R,5R absolute configuration. The resulting stereochemistry was confirmed by 1D- and 2D-NMR spectra of the acetonide product (Rychnovsky & Skalitzky, 1990), as well as by X-ray crystallography.
Polypropionates are a common moiety consisting of a stereodefined array of methyl and hydroxy substituents in an aliphatic chain. Their structure is found in various natural products, many of them possessing a wide range of biological activity (typically antibiotic, antitumor, antifungal, antiparasitic, among others) (Rohr, 2000). Different methodologies have been applied for their synthesis, although the aldol approach continues to be one of the most used methods (Li & Menche, 2009). An alternative approach to their synthesis is the regioselective cleavage of oxirane rings. The methodology developed in our lab consists of a reiterative sequence in which a disubstituted epoxide is regioselectively cleaved with either a propynylaluminum reagent (Dávila et al., 2007) or Grignard reagent (Rodríguez et al., 2006), followed by reduction (if needed), and further epoxidation of the newly formed alkene. In this methodology, the configuration of the hydroxyl functionality is determined by the configuration of the epoxide, while the syn/anti relative configuration of the methyl and hydroxyl groups is defined by the epoxide geometry. In this substrate controlled synthesis of the title compound, the configuration of the formed hydroxyl group was determined by the configuration of the substrate epoxide, while the anti relative configuration obtained between the formed hydroxyl and methyl group was due to the cis-geometry of the epoxide.