organic compounds
Methyl (2′S,3′S)-3,4-O-(2′,3′-dimethoxybutane-2′,3′-diyl)-α-L-rhamnopyranoside: a glycosyl acceptor
aDepartment of Chemistry, Chung-Yuan Christian University, Chung-Li 320, Taiwan
*Correspondence e-mail: tsaiyofu@cycu.edu.tw
The title compound, C13H24O7, is the product of the ketalization of methyl L-(+)-rhamnopyranoside with 2,3-butanedione. It crystallizes with two molecules in the which are connected by O—H⋯O hydrogen bonds. The C-3,4 diequatorial hydroxy groups of the methyl L-(+)-rhamnopyranoside were protected, leaving the C-2 hydroxy group free. The L-(+)-rhamnopyranoside and 2′,3′-dimethoxybutane-2′,3′-diyl rings adopt chair conformations and all methoxy groups are in axial positions. The was assumed from the synthesis.
Related literature
For related literature, see: Duynstee et al. (1998); Lang & Wullbrandt (1999); Leisinger & Margraff (1979); Montchamp et al. (1996); Bauer et al. (2006).
Experimental
Crystal data
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Refinement
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Data collection: XSCANS (Siemens, 1995); cell XSCANS; data reduction: SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536808008222/bt2683sup1.cif
contains datablock I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808008222/bt2683Isup2.hkl
A solution of methyl L-(+)-rhamnopyranose ([a]20D = + 8.2°) (638 mg, 3.58 mmol), trimeyhyl orthoformate (1.20 ml, 10.75 mmol) and 2,3-butanedione (0.35 ml, 3.98 mmol) in dried methanol (15 ml) was treated with camphersulfonic acid (50 mg, 0.22 mmol). The mixture was refluxed for 18 h. The cool reaction mixture was then treated with NEt3 and concentrated under reduced pressure to observe crude product. The crude product was purified via flash
on silica gel (EtOAc/n-hexane = 1:1) to obtain 874 mg (84%) of the title compound as white powder. The pure product was recrystalized from CH2Cl2 at room temperature.In the absence of anomalous scatterers Friedel pairs were merged prior to
The C-bound H atoms were placed in calculated positions (C—H = 0.96–0.98 Å) and included in the in the riding-model approximation, with Uiso(H) = 1.2 or 1.5Ueq(C). The hydroxy H atoms were constrained to ideal geometries with O(N)—H = 0.82 Å and Uiso(H) = 1.5Ueq(O).Data collection: XSCANS (Siemens, 1995); cell
XSCANS (Siemens, 1995); data reduction: SHELXTL (Sheldrick, 2008); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C13H24O7 | F(000) = 1264 |
Mr = 292.32 | Dx = 1.263 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 27 reflections |
a = 12.8743 (14) Å | θ = 5.1–12.5° |
b = 13.1182 (12) Å | µ = 0.10 mm−1 |
c = 18.208 (3) Å | T = 295 K |
V = 3075.0 (7) Å3 | Block, colourless |
Z = 8 | 0.6 × 0.5 × 0.4 mm |
Bruker P4 diffractometer | 2630 reflections with I > 2s(I) |
Radiation source: fine-focus sealed tube | Rint = 0.020 |
Graphite monochromator | θmax = 25.0°, θmin = 1.9° |
ω scans | h = −1→15 |
Absorption correction: ψ scan (North et al., 1968) | k = −1→15 |
Tmin = 0.933, Tmax = 0.994 | l = −1→21 |
3842 measured reflections | 3 standard reflections every 97 reflections |
3032 independent reflections | intensity decay: none |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.038 | H-atom parameters constrained |
wR(F2) = 0.106 | w = 1/[σ2(Fo2) + (0.0561P)2 + 0.7995P] where P = (Fo2 + 2Fc2)/3 |
S = 1.02 | (Δ/σ)max < 0.001 |
3032 reflections | Δρmax = 0.15 e Å−3 |
362 parameters | Δρmin = −0.17 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0063 (6) |
C13H24O7 | V = 3075.0 (7) Å3 |
Mr = 292.32 | Z = 8 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 12.8743 (14) Å | µ = 0.10 mm−1 |
b = 13.1182 (12) Å | T = 295 K |
c = 18.208 (3) Å | 0.6 × 0.5 × 0.4 mm |
Bruker P4 diffractometer | 2630 reflections with I > 2s(I) |
Absorption correction: ψ scan (North et al., 1968) | Rint = 0.020 |
Tmin = 0.933, Tmax = 0.994 | 3 standard reflections every 97 reflections |
3842 measured reflections | intensity decay: none |
3032 independent reflections |
R[F2 > 2σ(F2)] = 0.038 | 0 restraints |
wR(F2) = 0.106 | H-atom parameters constrained |
S = 1.02 | Δρmax = 0.15 e Å−3 |
3032 reflections | Δρmin = −0.17 e Å−3 |
362 parameters |
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. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.29481 (18) | 0.87985 (15) | 0.88054 (10) | 0.0505 (5) | |
O2 | 0.1553 (2) | 0.8215 (2) | 0.95033 (13) | 0.0673 (7) | |
O3 | 0.35887 (18) | 0.66974 (18) | 0.87880 (14) | 0.0614 (6) | |
O4 | 0.20071 (17) | 0.70426 (15) | 0.82239 (11) | 0.0469 (5) | |
O5 | 0.38039 (16) | 0.96048 (16) | 0.74810 (11) | 0.0502 (5) | |
H5A | 0.4138 | 0.9481 | 0.7854 | 0.075* | |
O6 | 0.11031 (18) | 0.99268 (18) | 0.71133 (13) | 0.0626 (6) | |
O7 | 0.21798 (18) | 0.86713 (17) | 0.66048 (11) | 0.0529 (5) | |
O8 | 0.38389 (15) | 0.21315 (15) | 0.83116 (10) | 0.0426 (4) | |
O9 | 0.38270 (19) | 0.33878 (17) | 0.92121 (12) | 0.0564 (6) | |
O10 | 0.17861 (17) | 0.16879 (17) | 0.87757 (12) | 0.0548 (5) | |
O11 | 0.20194 (17) | 0.33159 (15) | 0.82917 (10) | 0.0470 (5) | |
O12 | 0.37676 (17) | 0.15454 (15) | 0.67829 (11) | 0.0481 (5) | |
H12A | 0.3881 | 0.1110 | 0.7096 | 0.072* | |
O13 | 0.43863 (16) | 0.41769 (15) | 0.66158 (12) | 0.0515 (5) | |
O14 | 0.27898 (16) | 0.34098 (16) | 0.63634 (10) | 0.0451 (5) | |
C1 | 0.2596 (3) | 0.8024 (3) | 0.92943 (17) | 0.0570 (9) | |
C2 | 0.3345 (4) | 0.8045 (3) | 0.99348 (19) | 0.0829 (13) | |
H2A | 0.3352 | 0.8714 | 1.0148 | 0.124* | |
H2B | 0.4030 | 0.7875 | 0.9766 | 0.124* | |
H2C | 0.3129 | 0.7558 | 1.0298 | 0.124* | |
C3 | 0.1350 (4) | 0.9160 (3) | 0.9869 (2) | 0.0932 (15) | |
H3A | 0.0622 | 0.9210 | 0.9977 | 0.140* | |
H3B | 0.1551 | 0.9716 | 0.9557 | 0.140* | |
H3C | 0.1740 | 0.9188 | 1.0317 | 0.140* | |
C4 | 0.2534 (3) | 0.6969 (2) | 0.89081 (17) | 0.0507 (8) | |
C5 | 0.3743 (3) | 0.5765 (3) | 0.8392 (3) | 0.0899 (15) | |
H5B | 0.4473 | 0.5641 | 0.8335 | 0.135* | |
H5C | 0.3425 | 0.5817 | 0.7916 | 0.135* | |
H5D | 0.3433 | 0.5211 | 0.8659 | 0.135* | |
C6 | 0.1952 (3) | 0.6187 (3) | 0.9353 (2) | 0.0671 (10) | |
H6A | 0.1933 | 0.5553 | 0.9089 | 0.101* | |
H6B | 0.1256 | 0.6420 | 0.9438 | 0.101* | |
H6C | 0.2297 | 0.6088 | 0.9815 | 0.101* | |
C7 | 0.2429 (2) | 0.7820 (2) | 0.77618 (15) | 0.0426 (7) | |
H7A | 0.3160 | 0.7670 | 0.7659 | 0.051* | |
C8 | 0.2344 (2) | 0.8829 (2) | 0.81437 (15) | 0.0436 (7) | |
H8A | 0.1615 | 0.8952 | 0.8271 | 0.052* | |
C9 | 0.2721 (2) | 0.9686 (2) | 0.76624 (16) | 0.0438 (7) | |
H9A | 0.2589 | 1.0340 | 0.7904 | 0.053* | |
C10 | 0.2127 (3) | 0.9639 (2) | 0.69401 (17) | 0.0497 (7) | |
H10A | 0.2420 | 1.0145 | 0.6603 | 0.060* | |
C11 | 0.0474 (3) | 1.0130 (4) | 0.6492 (3) | 0.1003 (16) | |
H11A | −0.0209 | 1.0325 | 0.6651 | 0.150* | |
H11B | 0.0428 | 0.9529 | 0.6193 | 0.150* | |
H11C | 0.0776 | 1.0674 | 0.6211 | 0.150* | |
C12 | 0.1820 (3) | 0.7835 (2) | 0.70469 (16) | 0.0477 (7) | |
H12B | 0.1080 | 0.7924 | 0.7154 | 0.057* | |
C13 | 0.1975 (3) | 0.6876 (3) | 0.6604 (2) | 0.0698 (10) | |
H13A | 0.1575 | 0.6917 | 0.6160 | 0.105* | |
H13B | 0.1751 | 0.6298 | 0.6886 | 0.105* | |
H13C | 0.2697 | 0.6802 | 0.6484 | 0.105* | |
C14 | 0.3400 (3) | 0.2447 (2) | 0.89914 (15) | 0.0445 (7) | |
C15 | 0.3620 (3) | 0.1598 (3) | 0.95361 (17) | 0.0591 (9) | |
H15A | 0.4356 | 0.1497 | 0.9575 | 0.089* | |
H15B | 0.3297 | 0.0980 | 0.9370 | 0.089* | |
H15C | 0.3345 | 0.1780 | 1.0008 | 0.089* | |
C16 | 0.4938 (3) | 0.3455 (3) | 0.9215 (2) | 0.0743 (11) | |
H16A | 0.5144 | 0.4122 | 0.9375 | 0.111* | |
H16B | 0.5197 | 0.3335 | 0.8728 | 0.111* | |
H16C | 0.5216 | 0.2952 | 0.9544 | 0.111* | |
C17 | 0.2219 (3) | 0.2663 (2) | 0.89001 (16) | 0.0471 (7) | |
C18 | 0.0701 (3) | 0.1652 (3) | 0.8604 (2) | 0.0737 (11) | |
H18A | 0.0493 | 0.0956 | 0.8532 | 0.111* | |
H18B | 0.0574 | 0.2032 | 0.8162 | 0.111* | |
H18C | 0.0310 | 0.1943 | 0.9000 | 0.111* | |
C19 | 0.1755 (3) | 0.3204 (3) | 0.95614 (18) | 0.0642 (10) | |
H19A | 0.1028 | 0.3319 | 0.9479 | 0.096* | |
H19B | 0.2099 | 0.3845 | 0.9632 | 0.096* | |
H19C | 0.1844 | 0.2788 | 0.9991 | 0.096* | |
C20 | 0.2480 (2) | 0.2952 (2) | 0.76220 (15) | 0.0400 (6) | |
H20A | 0.2181 | 0.2290 | 0.7489 | 0.048* | |
C21 | 0.3632 (2) | 0.2850 (2) | 0.77310 (14) | 0.0388 (6) | |
H21A | 0.3917 | 0.3515 | 0.7869 | 0.047* | |
C22 | 0.4147 (2) | 0.2498 (2) | 0.70284 (15) | 0.0400 (6) | |
H22A | 0.4902 | 0.2467 | 0.7094 | 0.048* | |
C23 | 0.3874 (2) | 0.3265 (2) | 0.64348 (15) | 0.0425 (6) | |
H23A | 0.4147 | 0.3017 | 0.5965 | 0.051* | |
C24 | 0.4307 (3) | 0.4943 (3) | 0.6062 (2) | 0.0701 (10) | |
H24A | 0.4665 | 0.5546 | 0.6222 | 0.105* | |
H24B | 0.3589 | 0.5101 | 0.5978 | 0.105* | |
H24C | 0.4615 | 0.4699 | 0.5616 | 0.105* | |
C25 | 0.2258 (2) | 0.3727 (2) | 0.70230 (15) | 0.0430 (7) | |
H25A | 0.2511 | 0.4399 | 0.7175 | 0.052* | |
C26 | 0.1112 (3) | 0.3797 (3) | 0.6822 (2) | 0.0652 (10) | |
H26A | 0.1019 | 0.4304 | 0.6447 | 0.098* | |
H26B | 0.0718 | 0.3984 | 0.7249 | 0.098* | |
H26C | 0.0877 | 0.3149 | 0.6643 | 0.098* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0683 (14) | 0.0485 (11) | 0.0347 (10) | −0.0162 (11) | −0.0075 (10) | 0.0047 (9) |
O2 | 0.0860 (18) | 0.0663 (15) | 0.0495 (12) | −0.0112 (14) | 0.0156 (12) | −0.0026 (12) |
O3 | 0.0551 (14) | 0.0524 (12) | 0.0768 (15) | −0.0051 (11) | −0.0090 (12) | 0.0158 (12) |
O4 | 0.0527 (12) | 0.0444 (10) | 0.0436 (10) | −0.0123 (10) | −0.0050 (10) | 0.0060 (9) |
O5 | 0.0487 (12) | 0.0539 (12) | 0.0480 (11) | −0.0057 (10) | −0.0044 (10) | 0.0100 (10) |
O6 | 0.0520 (13) | 0.0695 (15) | 0.0662 (14) | 0.0071 (12) | −0.0070 (12) | 0.0189 (12) |
O7 | 0.0619 (13) | 0.0616 (13) | 0.0353 (10) | −0.0092 (11) | −0.0043 (10) | 0.0041 (10) |
O8 | 0.0487 (11) | 0.0449 (10) | 0.0341 (9) | 0.0091 (9) | −0.0015 (9) | 0.0017 (9) |
O9 | 0.0694 (15) | 0.0526 (12) | 0.0473 (11) | 0.0022 (12) | −0.0088 (11) | −0.0066 (11) |
O10 | 0.0536 (12) | 0.0520 (12) | 0.0587 (13) | 0.0000 (11) | 0.0034 (11) | 0.0075 (11) |
O11 | 0.0538 (12) | 0.0503 (11) | 0.0368 (9) | 0.0139 (10) | 0.0053 (9) | 0.0036 (9) |
O12 | 0.0582 (12) | 0.0424 (10) | 0.0436 (10) | −0.0060 (10) | 0.0036 (10) | −0.0028 (9) |
O13 | 0.0543 (12) | 0.0473 (11) | 0.0530 (12) | −0.0147 (10) | −0.0035 (11) | 0.0055 (10) |
O14 | 0.0481 (12) | 0.0549 (12) | 0.0323 (9) | −0.0046 (10) | −0.0023 (8) | 0.0026 (9) |
C1 | 0.071 (2) | 0.062 (2) | 0.0384 (15) | −0.0189 (18) | −0.0021 (16) | 0.0082 (14) |
C2 | 0.119 (3) | 0.086 (3) | 0.0434 (18) | −0.035 (3) | −0.025 (2) | 0.0195 (19) |
C3 | 0.131 (4) | 0.087 (3) | 0.062 (2) | −0.003 (3) | 0.024 (3) | −0.012 (2) |
C4 | 0.0558 (19) | 0.0491 (17) | 0.0472 (16) | −0.0094 (15) | −0.0059 (15) | 0.0139 (14) |
C5 | 0.069 (2) | 0.0473 (19) | 0.154 (5) | 0.0036 (19) | 0.001 (3) | 0.009 (3) |
C6 | 0.077 (2) | 0.063 (2) | 0.062 (2) | −0.025 (2) | −0.009 (2) | 0.0213 (17) |
C7 | 0.0476 (16) | 0.0417 (14) | 0.0384 (14) | −0.0063 (13) | −0.0001 (13) | 0.0035 (13) |
C8 | 0.0511 (17) | 0.0457 (15) | 0.0342 (14) | −0.0060 (13) | −0.0045 (13) | 0.0027 (13) |
C9 | 0.0492 (16) | 0.0419 (15) | 0.0401 (15) | −0.0013 (13) | −0.0001 (13) | 0.0040 (12) |
C10 | 0.0528 (18) | 0.0503 (17) | 0.0460 (16) | −0.0033 (15) | −0.0022 (15) | 0.0133 (14) |
C11 | 0.066 (3) | 0.142 (4) | 0.093 (3) | 0.003 (3) | −0.024 (2) | 0.051 (3) |
C12 | 0.0505 (17) | 0.0518 (16) | 0.0409 (15) | −0.0078 (15) | −0.0031 (14) | 0.0011 (14) |
C13 | 0.085 (3) | 0.069 (2) | 0.056 (2) | −0.006 (2) | −0.010 (2) | −0.0167 (18) |
C14 | 0.0571 (18) | 0.0438 (15) | 0.0327 (14) | 0.0051 (14) | −0.0022 (13) | −0.0014 (12) |
C15 | 0.077 (2) | 0.0559 (18) | 0.0441 (16) | 0.0182 (18) | −0.0011 (16) | 0.0077 (15) |
C16 | 0.074 (2) | 0.075 (2) | 0.074 (2) | −0.008 (2) | −0.031 (2) | 0.000 (2) |
C17 | 0.0574 (18) | 0.0465 (16) | 0.0373 (14) | 0.0096 (14) | 0.0063 (14) | 0.0057 (13) |
C18 | 0.054 (2) | 0.087 (3) | 0.080 (2) | −0.007 (2) | 0.0077 (18) | 0.008 (2) |
C19 | 0.080 (2) | 0.066 (2) | 0.0462 (17) | 0.018 (2) | 0.0168 (17) | 0.0049 (17) |
C20 | 0.0414 (15) | 0.0434 (15) | 0.0353 (14) | 0.0022 (13) | 0.0044 (12) | −0.0009 (12) |
C21 | 0.0415 (15) | 0.0402 (14) | 0.0347 (13) | 0.0003 (12) | −0.0029 (12) | 0.0028 (12) |
C22 | 0.0377 (14) | 0.0422 (15) | 0.0400 (14) | −0.0043 (12) | −0.0001 (12) | −0.0015 (12) |
C23 | 0.0424 (15) | 0.0470 (15) | 0.0381 (14) | −0.0050 (14) | 0.0016 (12) | −0.0020 (13) |
C24 | 0.092 (3) | 0.057 (2) | 0.062 (2) | −0.020 (2) | 0.002 (2) | 0.0159 (17) |
C25 | 0.0452 (16) | 0.0478 (16) | 0.0361 (14) | 0.0033 (13) | −0.0030 (13) | 0.0012 (12) |
C26 | 0.0502 (19) | 0.089 (3) | 0.057 (2) | 0.0166 (19) | −0.0059 (16) | 0.0103 (19) |
O1—C1 | 1.425 (4) | C7—H7A | 0.9800 |
O1—C8 | 1.434 (3) | C8—C9 | 1.505 (4) |
O2—C1 | 1.419 (4) | C8—H8A | 0.9800 |
O2—C3 | 1.430 (5) | C9—C10 | 1.523 (4) |
O3—C4 | 1.421 (4) | C9—H9A | 0.9800 |
O3—C5 | 1.434 (5) | C10—H10A | 0.9800 |
O4—C4 | 1.422 (4) | C11—H11A | 0.9600 |
O4—C7 | 1.429 (3) | C11—H11B | 0.9600 |
O5—C9 | 1.437 (4) | C11—H11C | 0.9600 |
O5—H5A | 0.8200 | C12—C13 | 1.508 (5) |
O6—C10 | 1.407 (4) | C12—H12B | 0.9800 |
O6—C11 | 1.417 (5) | C13—H13A | 0.9600 |
O7—C10 | 1.410 (4) | C13—H13B | 0.9600 |
O7—C12 | 1.437 (4) | C13—H13C | 0.9600 |
O8—C14 | 1.423 (3) | C14—C15 | 1.519 (4) |
O8—C21 | 1.441 (3) | C14—C17 | 1.555 (4) |
O9—C14 | 1.409 (4) | C15—H15A | 0.9600 |
O9—C16 | 1.433 (4) | C15—H15B | 0.9600 |
O10—C17 | 1.414 (4) | C15—H15C | 0.9600 |
O10—C18 | 1.432 (4) | C16—H16A | 0.9600 |
O11—C17 | 1.424 (3) | C16—H16B | 0.9600 |
O11—C20 | 1.438 (3) | C16—H16C | 0.9600 |
O12—C22 | 1.414 (3) | C17—C19 | 1.520 (4) |
O12—H12A | 0.8200 | C18—H18A | 0.9600 |
O13—C23 | 1.406 (3) | C18—H18B | 0.9600 |
O13—C24 | 1.427 (4) | C18—H18C | 0.9600 |
O14—C23 | 1.415 (4) | C19—H19A | 0.9600 |
O14—C25 | 1.444 (3) | C19—H19B | 0.9600 |
C1—C2 | 1.513 (5) | C19—H19C | 0.9600 |
C1—C4 | 1.555 (5) | C20—C21 | 1.501 (4) |
C2—H2A | 0.9600 | C20—C25 | 1.519 (4) |
C2—H2B | 0.9600 | C20—H20A | 0.9800 |
C2—H2C | 0.9600 | C21—C22 | 1.514 (4) |
C3—H3A | 0.9600 | C21—H21A | 0.9800 |
C3—H3B | 0.9600 | C22—C23 | 1.518 (4) |
C3—H3C | 0.9600 | C22—H22A | 0.9800 |
C4—C6 | 1.507 (4) | C23—H23A | 0.9800 |
C5—H5B | 0.9600 | C24—H24A | 0.9600 |
C5—H5C | 0.9600 | C24—H24B | 0.9600 |
C5—H5D | 0.9600 | C24—H24C | 0.9600 |
C6—H6A | 0.9600 | C25—C26 | 1.522 (4) |
C6—H6B | 0.9600 | C25—H25A | 0.9800 |
C6—H6C | 0.9600 | C26—H26A | 0.9600 |
C7—C8 | 1.500 (4) | C26—H26B | 0.9600 |
C7—C12 | 1.519 (4) | C26—H26C | 0.9600 |
C1—O1—C8 | 111.9 (2) | C7—C12—H12B | 109.5 |
C1—O2—C3 | 116.8 (3) | C12—C13—H13A | 109.5 |
C4—O3—C5 | 115.0 (3) | C12—C13—H13B | 109.5 |
C4—O4—C7 | 112.5 (2) | H13A—C13—H13B | 109.5 |
C9—O5—H5A | 109.5 | C12—C13—H13C | 109.5 |
C10—O6—C11 | 114.0 (3) | H13A—C13—H13C | 109.5 |
C10—O7—C12 | 115.4 (2) | H13B—C13—H13C | 109.5 |
C14—O8—C21 | 112.0 (2) | O9—C14—O8 | 110.4 (2) |
C14—O9—C16 | 116.4 (3) | O9—C14—C15 | 112.5 (2) |
C17—O10—C18 | 116.7 (3) | O8—C14—C15 | 106.3 (2) |
C17—O11—C20 | 112.7 (2) | O9—C14—C17 | 104.6 (2) |
C22—O12—H12A | 109.5 | O8—C14—C17 | 110.4 (2) |
C23—O13—C24 | 113.6 (2) | C15—C14—C17 | 112.7 (3) |
C23—O14—C25 | 115.5 (2) | C14—C15—H15A | 109.5 |
O2—C1—O1 | 110.0 (3) | C14—C15—H15B | 109.5 |
O2—C1—C2 | 113.2 (3) | H15A—C15—H15B | 109.5 |
O1—C1—C2 | 105.4 (3) | C14—C15—H15C | 109.5 |
O2—C1—C4 | 103.3 (3) | H15A—C15—H15C | 109.5 |
O1—C1—C4 | 111.7 (2) | H15B—C15—H15C | 109.5 |
C2—C1—C4 | 113.4 (3) | O9—C16—H16A | 109.5 |
C1—C2—H2A | 109.5 | O9—C16—H16B | 109.5 |
C1—C2—H2B | 109.5 | H16A—C16—H16B | 109.5 |
H2A—C2—H2B | 109.5 | O9—C16—H16C | 109.5 |
C1—C2—H2C | 109.5 | H16A—C16—H16C | 109.5 |
H2A—C2—H2C | 109.5 | H16B—C16—H16C | 109.5 |
H2B—C2—H2C | 109.5 | O10—C17—O11 | 110.4 (3) |
O2—C3—H3A | 109.5 | O10—C17—C19 | 113.2 (3) |
O2—C3—H3B | 109.5 | O11—C17—C19 | 105.4 (2) |
H3A—C3—H3B | 109.5 | O10—C17—C14 | 103.8 (2) |
O2—C3—H3C | 109.5 | O11—C17—C14 | 111.7 (2) |
H3A—C3—H3C | 109.5 | C19—C17—C14 | 112.6 (3) |
H3B—C3—H3C | 109.5 | O10—C18—H18A | 109.5 |
O3—C4—O4 | 109.8 (3) | O10—C18—H18B | 109.5 |
O3—C4—C6 | 112.8 (3) | H18A—C18—H18B | 109.5 |
O4—C4—C6 | 106.3 (3) | O10—C18—H18C | 109.5 |
O3—C4—C1 | 104.1 (3) | H18A—C18—H18C | 109.5 |
O4—C4—C1 | 111.1 (2) | H18B—C18—H18C | 109.5 |
C6—C4—C1 | 112.9 (3) | C17—C19—H19A | 109.5 |
O3—C5—H5B | 109.5 | C17—C19—H19B | 109.5 |
O3—C5—H5C | 109.5 | H19A—C19—H19B | 109.5 |
H5B—C5—H5C | 109.5 | C17—C19—H19C | 109.5 |
O3—C5—H5D | 109.5 | H19A—C19—H19C | 109.5 |
H5B—C5—H5D | 109.5 | H19B—C19—H19C | 109.5 |
H5C—C5—H5D | 109.5 | O11—C20—C21 | 109.0 (2) |
C4—C6—H6A | 109.5 | O11—C20—C25 | 108.0 (2) |
C4—C6—H6B | 109.5 | C21—C20—C25 | 109.9 (2) |
H6A—C6—H6B | 109.5 | O11—C20—H20A | 110.0 |
C4—C6—H6C | 109.5 | C21—C20—H20A | 110.0 |
H6A—C6—H6C | 109.5 | C25—C20—H20A | 110.0 |
H6B—C6—H6C | 109.5 | O8—C21—C20 | 109.8 (2) |
O4—C7—C8 | 109.2 (2) | O8—C21—C22 | 109.8 (2) |
O4—C7—C12 | 108.5 (2) | C20—C21—C22 | 110.4 (2) |
C8—C7—C12 | 110.4 (2) | O8—C21—H21A | 108.9 |
O4—C7—H7A | 109.6 | C20—C21—H21A | 108.9 |
C8—C7—H7A | 109.6 | C22—C21—H21A | 108.9 |
C12—C7—H7A | 109.6 | O12—C22—C21 | 112.7 (2) |
O1—C8—C9 | 109.6 (2) | O12—C22—C23 | 106.3 (2) |
O1—C8—C7 | 109.0 (2) | C21—C22—C23 | 107.3 (2) |
C9—C8—C7 | 111.5 (2) | O12—C22—H22A | 110.2 |
O1—C8—H8A | 108.9 | C21—C22—H22A | 110.2 |
C9—C8—H8A | 108.9 | C23—C22—H22A | 110.2 |
C7—C8—H8A | 108.9 | O13—C23—O14 | 111.7 (2) |
O5—C9—C8 | 113.0 (2) | O13—C23—C22 | 106.8 (2) |
O5—C9—C10 | 106.6 (2) | O14—C23—C22 | 112.5 (2) |
C8—C9—C10 | 108.1 (2) | O13—C23—H23A | 108.6 |
O5—C9—H9A | 109.7 | O14—C23—H23A | 108.6 |
C8—C9—H9A | 109.7 | C22—C23—H23A | 108.6 |
C10—C9—H9A | 109.7 | O13—C24—H24A | 109.5 |
O7—C10—O6 | 112.6 (3) | O13—C24—H24B | 109.5 |
O7—C10—C9 | 112.7 (2) | H24A—C24—H24B | 109.5 |
O6—C10—C9 | 105.4 (3) | O13—C24—H24C | 109.5 |
O7—C10—H10A | 108.6 | H24A—C24—H24C | 109.5 |
O6—C10—H10A | 108.6 | H24B—C24—H24C | 109.5 |
C9—C10—H10A | 108.6 | O14—C25—C20 | 108.3 (2) |
O6—C11—H11A | 109.5 | O14—C25—C26 | 106.1 (2) |
O6—C11—H11B | 109.5 | C20—C25—C26 | 113.3 (3) |
H11A—C11—H11B | 109.5 | O14—C25—H25A | 109.7 |
O6—C11—H11C | 109.5 | C20—C25—H25A | 109.7 |
H11A—C11—H11C | 109.5 | C26—C25—H25A | 109.7 |
H11B—C11—H11C | 109.5 | C25—C26—H26A | 109.5 |
O7—C12—C13 | 107.1 (3) | C25—C26—H26B | 109.5 |
O7—C12—C7 | 108.9 (2) | H26A—C26—H26B | 109.5 |
C13—C12—C7 | 112.3 (3) | C25—C26—H26C | 109.5 |
O7—C12—H12B | 109.5 | H26A—C26—H26C | 109.5 |
C13—C12—H12B | 109.5 | H26B—C26—H26C | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O13i | 0.82 | 2.17 | 2.907 (3) | 150 |
O12—H12A···O5ii | 0.82 | 2.10 | 2.846 (3) | 152 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, y−1, z. |
Experimental details
Crystal data | |
Chemical formula | C13H24O7 |
Mr | 292.32 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 295 |
a, b, c (Å) | 12.8743 (14), 13.1182 (12), 18.208 (3) |
V (Å3) | 3075.0 (7) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.6 × 0.5 × 0.4 |
Data collection | |
Diffractometer | Bruker P4 diffractometer |
Absorption correction | ψ scan (North et al., 1968) |
Tmin, Tmax | 0.933, 0.994 |
No. of measured, independent and observed [I > 2s(I)] reflections | 3842, 3032, 2630 |
Rint | 0.020 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.106, 1.02 |
No. of reflections | 3032 |
No. of parameters | 362 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.15, −0.17 |
Computer programs: XSCANS (Siemens, 1995), SHELXTL (Sheldrick, 2008), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008).
D—H···A | D—H | H···A | D···A | D—H···A |
O5—H5A···O13i | 0.8200 | 2.1700 | 2.907 (3) | 150.00 |
O12—H12A···O5ii | 0.8200 | 2.1000 | 2.846 (3) | 152.00 |
Symmetry codes: (i) −x+1, y+1/2, −z+3/2; (ii) x, y−1, z. |
Acknowledgements
We gratefully acknowledge financial support in part from the National Science Council, Taiwan (NSC 96-2113-M-033-003) and in part from the Project of the Specific Research Fields of Chung Yuan Christian University, Taiwan (CYCU-95-CR-CH).
References
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L-Rhamnopyranse-containing glycolipids display a wide range of biological properties (Leisinger, & Margraff, 1979; Lang & Wullbrandt, 1999; Bauer et al., 2006). For the above reason, we were interesting to study on the total synthesis of rhamnolipids. The title compound, C13H24O7, which was synthesized by the ketalization of C-3,4 hydroxyl group of the methyl L-(+)-rhamnopyranoside, with 2,3-butanedione and chemoselectively protected the C-3,4 diequatorial hydroxyl group (Montchamp et al., 1996; Duynstee et al., 1998), was utilized as glycosyl acceptor in our synthetic strategy. The methyl L-(+)-rhamnopyranoside was prepared by acetalization of the commercial optical pure L-(+)-rhamnopyranose as starting material with methanol. The structure of L-rhamnopyranoside ring and 2',3'-dimethoxybutan-2',3'-diyl ring are chair conformation and all of methoxy groups are at axial position.