Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680503031X/is6126sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680503031X/is6126Isup2.hkl |
CCDC reference: 287612
Key indicators
- Single-crystal X-ray study
- T = 193 K
- Mean (C-C) = 0.003 Å
- R factor = 0.027
- wR factor = 0.049
- Data-to-parameter ratio = 13.4
checkCIF/PLATON results
No syntax errors found
Alert level B PLAT222_ALERT_3_B Large Non-Solvent H Ueq(max)/Ueq(min) ... 4.88 Ratio PLAT231_ALERT_4_B Hirshfeld Test (Solvent) C30 - C36 .. 10.00 su
Alert level C PLAT231_ALERT_4_C Hirshfeld Test (Solvent) C30 - C31 .. 6.60 su PLAT231_ALERT_4_C Hirshfeld Test (Solvent) C30 - C35 .. 5.05 su PLAT231_ALERT_4_C Hirshfeld Test (Solvent) C33 - C34 .. 7.03 su
Alert level G REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 25.97 From the CIF: _reflns_number_total 5724 Count of symmetry unique reflns 3269 Completeness (_total/calc) 175.10% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 2455 Fraction of Friedel pairs measured 0.751 Are heavy atom types Z>Si present yes
0 ALERT level A = In general: serious problem 2 ALERT level B = Potentially serious problem 3 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 1 ALERT type 3 Indicator that the structure quality may be low 5 ALERT type 4 Improvement, methodology, query or suggestion
The title compound was prepared from (3aS,4S,4aS,7R,9S,9aS)-4-hydroxy-9-methanesulfonyloxy-2,2-dimethyl-8-oxo-octahydro-1,3-dioxa-5-thia-7a-azacyclopenta[f]azulene-7-carboxylic acid methyl ester (1.33 g, 3.25 mmol) by treatment with benzylbromide (1.67 g, 9.75 mmol), sodium hydride (0.12 g, 4.88 mmol) and tetrabutylammonium iodide (20 mg, 0.05 mmol) in dimethylformamide (70 ml) for 3 h at room temperature. Water (200 ml) was added and the reaction mixture was extracted twice with toluene. After removal of the organic solvent, the desired product was purified by flash chromatography. Colourless crystals of (I) were obtained by recrystallization from ethyl acetate (yield: 1.06 g, 2.11 mmol, 65%). Spectroscopic analysis: 1H NMR (500 MHz, DMSO-d6, δ, p.p.m.): 7.38–7.28 (m, 5 H, Ph), 5.30 (s, 1 H, 9a-H), 5.27 (s, 1 H, 6-H), 5.06 (d, 3J3-H,2'-H = 6.80 Hz, 1 H, 3-H), 4.90 (d, 2JBn = 11.21 Hz, 1 H, Ph—CH2), 4.73 (d, 2JBn = 11.21 Hz, 1 H, Ph—CH2), 4.30 (d, 3J9-H,8-H = 2.24 Hz, 1 H, 9-H), 4.26 (dd, 3J8-H,7-H = 9.45 Hz, 3J8-H,9-H = 2.24 Hz, 1 H, 8-H), 4.15 (dd, 3J7-H,8-H = 9.45 Hz, 3J7-H,6-H = 1 Hz, 1 H, 7-H), 3.64 (s, 3 H, OCH3), 3.37 (dd, 2J2'-H,2-H = 11.76 Hz, 3J2'-H,3-H = 7.00 Hz, 1 H, 2'-H), 3.29 (s, 3 H, SCH3), 3.09 (d, 2J2-H,2'-H = 11.76 Hz, 1 H, 2-H), 1.39 (ps, 6 H, CH3). 13C NMR (125 MHz, DMSO-d6, δ, p.p.m.): 169.24, 163.02 (CO), 137.93, 128.30, 127.82, 127.71 (Ph), 108.61 (CqIsopr), 80.51 (9-C), 78.10 (6-C), 76.23 (8-C), 75.11 (CH2—Ph), 70.47 (7-C), 65.63 (3-C), 60.84 (9a-C), 52.43 (OCH3), 38.59 (SCH3), 30.47 (2-C), 26.33, 26.24 (CH3Isopr).
Methyl groups and solvent aromatic H atoms were refined with idealized geometry [for Me H, C—H = 0.98 Å, H—C—H = 109.5° and Uiso(H) = 1.5Ueq(C), with torsion angles from the electron density; for solvent CH, C—H = 0.98 Å, H on the external bisector, Uiso(H) = 1.2Ueq(C)]. All other H atoms were located and refined isotropically. The bond length range is 0.87 (2)–1.07 (2) Å. The absolute structure was determined via the refinement of an inversion twin.
Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: DIAMOND (Brandenburg, 2004); software used to prepare material for publication: WinGX (Farrugia, 1999).
C21H27NO9S2·C7H8 | F(000) = 1256 |
Mr = 593.69 | Dx = 1.339 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 21120 reflections |
a = 10.1251 (6) Å | θ = 1.6–26.2° |
b = 11.4082 (5) Å | µ = 0.23 mm−1 |
c = 25.4972 (15) Å | T = 193 K |
V = 2945.2 (3) Å3 | Plate, colourless |
Z = 4 | 0.4 × 0.4 × 0.05 mm |
Stoe IPDS 2 diffractometer | Rint = 0.037 |
ω scans | θmax = 26.0°, θmin = 1.6° |
29561 measured reflections | h = −12→12 |
5724 independent reflections | k = −14→14 |
4668 reflections with I > 2σ(I) | l = −31→31 |
Refinement on F2 | H atoms treated by a mixture of independent and constrained refinement |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0245P)2] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.027 | (Δ/σ)max = 0.001 |
wR(F2) = 0.049 | Δρmax = 0.14 e Å−3 |
S = 0.89 | Δρmin = −0.18 e Å−3 |
5724 reflections | Absolute structure: Flack (1983), with 2479 Friedel pairs |
426 parameters | Absolute structure parameter: 0.02 (4) |
0 restraints |
C21H27NO9S2·C7H8 | V = 2945.2 (3) Å3 |
Mr = 593.69 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 10.1251 (6) Å | µ = 0.23 mm−1 |
b = 11.4082 (5) Å | T = 193 K |
c = 25.4972 (15) Å | 0.4 × 0.4 × 0.05 mm |
Stoe IPDS 2 diffractometer | 4668 reflections with I > 2σ(I) |
29561 measured reflections | Rint = 0.037 |
5724 independent reflections |
R[F2 > 2σ(F2)] = 0.027 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.049 | Δρmax = 0.14 e Å−3 |
S = 0.89 | Δρmin = −0.18 e Å−3 |
5724 reflections | Absolute structure: Flack (1983), with 2479 Friedel pairs |
426 parameters | Absolute structure parameter: 0.02 (4) |
0 restraints |
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 | ||
C2 | 0.85020 (18) | 0.77782 (18) | 0.95213 (7) | 0.0327 (4) | |
C3 | 0.77303 (18) | 0.81284 (15) | 1.00038 (6) | 0.0284 (4) | |
C5 | 0.66584 (16) | 0.99122 (15) | 1.02784 (6) | 0.0274 (4) | |
C6 | 0.65173 (15) | 1.12417 (16) | 1.03027 (6) | 0.0257 (4) | |
C7 | 0.65328 (16) | 1.18138 (15) | 0.97693 (7) | 0.0258 (4) | |
C8 | 0.78920 (15) | 1.19366 (14) | 0.95286 (7) | 0.0260 (4) | |
C9 | 0.84404 (15) | 1.08227 (14) | 0.92964 (6) | 0.0240 (4) | |
C9A | 0.87964 (15) | 0.99958 (15) | 0.97450 (7) | 0.0254 (4) | |
C10 | 0.84174 (16) | 0.77455 (16) | 1.05094 (7) | 0.0309 (4) | |
C11 | 0.9268 (2) | 0.6090 (2) | 1.09615 (8) | 0.0554 (6) | |
H11A | 1.021 | 0.6278 | 1.0937 | 0.083* | |
H11B | 0.9152 | 0.5237 | 1.0961 | 0.083* | |
H11C | 0.8908 | 0.6417 | 1.1287 | 0.083* | |
C12 | 0.7384 (2) | 1.07822 (18) | 1.15471 (7) | 0.0494 (5) | |
H12A | 0.8265 | 1.044 | 1.1501 | 0.074* | |
H12B | 0.6717 | 1.0242 | 1.1408 | 0.074* | |
H12C | 0.722 | 1.0917 | 1.1921 | 0.074* | |
C13 | 0.68236 (15) | 1.36643 (16) | 0.94038 (6) | 0.0310 (4) | |
C14 | 0.59257 (19) | 1.41538 (19) | 0.89905 (8) | 0.0451 (5) | |
H14A | 0.6454 | 1.4545 | 0.872 | 0.068* | |
H14B | 0.532 | 1.4721 | 0.915 | 0.068* | |
H14C | 0.5417 | 1.3516 | 0.8831 | 0.068* | |
C15 | 0.76028 (19) | 1.45711 (16) | 0.96994 (8) | 0.0481 (5) | |
H15A | 0.8127 | 1.4187 | 0.9973 | 0.072* | |
H15B | 0.6996 | 1.5135 | 0.9861 | 0.072* | |
H15C | 0.8193 | 1.4983 | 0.9457 | 0.072* | |
C16 | 0.7629 (2) | 1.0592 (2) | 0.84192 (7) | 0.0407 (5) | |
C17 | 0.67606 (17) | 0.97882 (16) | 0.81073 (6) | 0.0317 (4) | |
C18 | 0.7155 (2) | 0.86566 (19) | 0.79949 (7) | 0.0438 (5) | |
C19 | 0.6336 (2) | 0.7906 (2) | 0.77242 (9) | 0.0529 (6) | |
C20 | 0.5112 (2) | 0.8287 (2) | 0.75569 (8) | 0.0500 (6) | |
C21 | 0.4712 (2) | 0.9403 (2) | 0.76620 (8) | 0.0490 (5) | |
C22 | 0.5527 (2) | 1.0145 (2) | 0.79395 (8) | 0.0420 (5) | |
C30 | 0.89040 (19) | 0.4904 (2) | 0.78038 (9) | 0.0551 (6) | |
C31 | 0.8776 (2) | 0.3675 (2) | 0.78532 (10) | 0.0592 (7) | |
H31 | 0.8773 | 0.3325 | 0.8191 | 0.071* | |
C32 | 0.8657 (2) | 0.2987 (3) | 0.74165 (11) | 0.0697 (7) | |
H32 | 0.8581 | 0.2162 | 0.7457 | 0.084* | |
C33 | 0.8646 (2) | 0.3454 (3) | 0.69237 (11) | 0.0694 (7) | |
H33 | 0.8559 | 0.2965 | 0.6624 | 0.083* | |
C34 | 0.8763 (2) | 0.4653 (2) | 0.68713 (10) | 0.0573 (6) | |
H34 | 0.8753 | 0.4987 | 0.653 | 0.069* | |
C35 | 0.88932 (19) | 0.5379 (2) | 0.72985 (9) | 0.0522 (6) | |
H35 | 0.8976 | 0.6202 | 0.725 | 0.063* | |
C36 | 0.9004 (3) | 0.5663 (3) | 0.82670 (10) | 0.0774 (8) | |
H36A | 0.9671 | 0.6269 | 0.8205 | 0.116* | |
H36B | 0.926 | 0.5192 | 0.8572 | 0.116* | |
H36C | 0.8147 | 0.6034 | 0.8334 | 0.116* | |
N4 | 0.76355 (12) | 0.94071 (11) | 0.99905 (5) | 0.0260 (3) | |
O1 | 0.85730 (13) | 0.65943 (11) | 1.05137 (5) | 0.0436 (3) | |
O2 | 0.87554 (15) | 0.83954 (12) | 1.08513 (6) | 0.0547 (4) | |
O3 | 0.58434 (11) | 0.93119 (11) | 1.05154 (5) | 0.0393 (3) | |
O4 | 0.75838 (11) | 1.17361 (9) | 1.06204 (4) | 0.0297 (3) | |
O5 | 0.83811 (13) | 1.28422 (13) | 1.13417 (5) | 0.0481 (3) | |
O6 | 0.59851 (13) | 1.25617 (13) | 1.12440 (5) | 0.0504 (4) | |
O7 | 0.76835 (11) | 1.28370 (10) | 0.91533 (4) | 0.0297 (2) | |
O8 | 0.60683 (10) | 1.29935 (11) | 0.97846 (4) | 0.0311 (3) | |
O9 | 0.75513 (10) | 1.02311 (10) | 0.89575 (4) | 0.0276 (3) | |
S1 | 0.98560 (4) | 0.88067 (4) | 0.951666 (19) | 0.03503 (11) | |
S2 | 0.72970 (4) | 1.21124 (4) | 1.120997 (17) | 0.03626 (11) | |
H2A | 0.7945 (15) | 0.7885 (15) | 0.9224 (6) | 0.029 (4)* | |
H2B | 0.8819 (15) | 0.7044 (16) | 0.9560 (6) | 0.025 (4)* | |
H3 | 0.6866 (15) | 0.7838 (15) | 1.0003 (6) | 0.021 (4)* | |
H6 | 0.5732 (15) | 1.1390 (13) | 1.0478 (6) | 0.019 (4)* | |
H7 | 0.5990 (14) | 1.1384 (14) | 0.9551 (6) | 0.018 (4)* | |
H8 | 0.8501 (15) | 1.2212 (14) | 0.9781 (6) | 0.017 (4)* | |
H9 | 0.9279 (15) | 1.1005 (14) | 0.9112 (6) | 0.019 (4)* | |
H9A | 0.9303 (14) | 1.0440 (15) | 1.0018 (6) | 0.026 (4)* | |
H16A | 0.725 (2) | 1.146 (2) | 0.8388 (8) | 0.069 (7)* | |
H16B | 0.8536 (19) | 1.0503 (17) | 0.8334 (8) | 0.044 (6)* | |
H18 | 0.800 (2) | 0.8411 (18) | 0.8093 (8) | 0.053 (6)* | |
H19 | 0.6686 (19) | 0.715 (2) | 0.7642 (7) | 0.052 (6)* | |
H20 | 0.455 (2) | 0.778 (2) | 0.7372 (9) | 0.064 (7)* | |
H21 | 0.385 (2) | 0.968 (2) | 0.7547 (9) | 0.071 (7)* | |
H22 | 0.528 (2) | 1.086 (2) | 0.8011 (8) | 0.057 (7)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C2 | 0.0404 (10) | 0.0255 (11) | 0.0323 (9) | 0.0045 (9) | −0.0041 (8) | 0.0002 (9) |
C3 | 0.0296 (8) | 0.0215 (10) | 0.0341 (9) | −0.0030 (8) | −0.0027 (7) | −0.0001 (7) |
C5 | 0.0258 (8) | 0.0293 (10) | 0.0272 (9) | −0.0032 (8) | −0.0021 (7) | −0.0003 (8) |
C6 | 0.0204 (8) | 0.0283 (10) | 0.0286 (9) | −0.0035 (8) | 0.0015 (7) | −0.0031 (8) |
C7 | 0.0246 (8) | 0.0227 (10) | 0.0301 (9) | 0.0004 (7) | −0.0012 (7) | −0.0027 (8) |
C8 | 0.0258 (8) | 0.0256 (10) | 0.0266 (8) | −0.0010 (7) | 0.0004 (7) | 0.0017 (8) |
C9 | 0.0225 (8) | 0.0224 (9) | 0.0271 (8) | −0.0031 (7) | 0.0016 (7) | 0.0003 (7) |
C9A | 0.0215 (8) | 0.0253 (10) | 0.0294 (9) | −0.0012 (7) | 0.0021 (7) | −0.0021 (8) |
C10 | 0.0356 (9) | 0.0247 (10) | 0.0325 (9) | −0.0024 (8) | −0.0010 (8) | 0.0024 (9) |
C11 | 0.0754 (15) | 0.0443 (14) | 0.0466 (12) | 0.0169 (12) | −0.0140 (10) | 0.0123 (11) |
C12 | 0.0553 (12) | 0.0556 (14) | 0.0374 (11) | −0.0044 (11) | 0.0028 (10) | 0.0076 (9) |
C13 | 0.0302 (8) | 0.0251 (10) | 0.0376 (10) | 0.0032 (7) | 0.0075 (7) | 0.0014 (8) |
C14 | 0.0425 (11) | 0.0447 (13) | 0.0481 (12) | 0.0128 (9) | 0.0087 (9) | 0.0117 (10) |
C15 | 0.0455 (11) | 0.0334 (11) | 0.0655 (13) | −0.0043 (9) | 0.0129 (10) | −0.0141 (10) |
C16 | 0.0495 (13) | 0.0443 (13) | 0.0283 (9) | −0.0111 (11) | 0.0000 (9) | 0.0042 (8) |
C17 | 0.0410 (10) | 0.0329 (11) | 0.0212 (8) | −0.0040 (8) | 0.0017 (8) | 0.0022 (8) |
C18 | 0.0429 (11) | 0.0482 (14) | 0.0402 (11) | 0.0094 (10) | −0.0042 (9) | −0.0076 (10) |
C19 | 0.0631 (14) | 0.0418 (14) | 0.0539 (13) | 0.0080 (12) | −0.0017 (11) | −0.0179 (12) |
C20 | 0.0483 (13) | 0.0577 (15) | 0.0442 (12) | −0.0108 (12) | −0.0051 (10) | −0.0133 (11) |
C21 | 0.0393 (11) | 0.0589 (16) | 0.0487 (13) | 0.0010 (11) | −0.0054 (10) | 0.0015 (11) |
C22 | 0.0522 (13) | 0.0354 (13) | 0.0384 (11) | 0.0061 (10) | 0.0041 (9) | 0.0015 (10) |
C30 | 0.0312 (10) | 0.084 (2) | 0.0502 (14) | 0.0045 (11) | 0.0037 (10) | 0.0075 (13) |
C31 | 0.0446 (12) | 0.0732 (19) | 0.0598 (15) | 0.0114 (12) | 0.0050 (10) | 0.0339 (14) |
C32 | 0.0611 (15) | 0.0672 (18) | 0.0808 (19) | 0.0167 (14) | 0.0144 (13) | 0.0118 (16) |
C33 | 0.0625 (15) | 0.079 (2) | 0.0672 (17) | 0.0171 (13) | 0.0114 (12) | 0.0105 (14) |
C34 | 0.0505 (13) | 0.0657 (18) | 0.0556 (15) | 0.0074 (11) | 0.0090 (11) | 0.0172 (13) |
C35 | 0.0397 (11) | 0.0627 (16) | 0.0541 (14) | 0.0029 (11) | 0.0042 (10) | 0.0218 (12) |
C36 | 0.0655 (16) | 0.097 (2) | 0.0693 (17) | −0.0131 (16) | −0.0042 (13) | 0.0162 (16) |
N4 | 0.0267 (7) | 0.0220 (8) | 0.0292 (7) | −0.0008 (6) | 0.0012 (6) | 0.0021 (6) |
O1 | 0.0628 (8) | 0.0268 (7) | 0.0413 (7) | 0.0081 (6) | −0.0141 (7) | 0.0042 (6) |
O2 | 0.0842 (11) | 0.0358 (9) | 0.0442 (8) | −0.0022 (7) | −0.0251 (8) | −0.0029 (7) |
O3 | 0.0376 (6) | 0.0324 (7) | 0.0480 (8) | −0.0086 (6) | 0.0133 (6) | 0.0015 (6) |
O4 | 0.0289 (6) | 0.0320 (6) | 0.0284 (6) | −0.0012 (5) | −0.0007 (5) | −0.0053 (5) |
O5 | 0.0570 (8) | 0.0433 (9) | 0.0440 (8) | −0.0089 (7) | −0.0095 (7) | −0.0127 (7) |
O6 | 0.0472 (8) | 0.0609 (10) | 0.0431 (8) | 0.0171 (7) | 0.0035 (7) | −0.0149 (7) |
O7 | 0.0332 (6) | 0.0215 (6) | 0.0342 (6) | 0.0035 (6) | 0.0054 (5) | 0.0033 (5) |
O8 | 0.0295 (6) | 0.0251 (7) | 0.0386 (7) | 0.0039 (5) | 0.0069 (5) | 0.0008 (6) |
O9 | 0.0306 (6) | 0.0287 (6) | 0.0236 (5) | −0.0037 (5) | 0.0010 (5) | −0.0005 (5) |
S1 | 0.0315 (2) | 0.0287 (2) | 0.0449 (3) | 0.0069 (2) | 0.0058 (2) | 0.0030 (2) |
S2 | 0.0406 (2) | 0.0381 (3) | 0.0300 (2) | 0.0029 (2) | −0.0011 (2) | −0.0076 (2) |
C2—C3 | 1.511 (2) | C14—H14A | 0.98 |
C2—S1 | 1.8046 (19) | C14—H14B | 0.98 |
C2—H2A | 0.953 (16) | C14—H14C | 0.98 |
C2—H2B | 0.902 (18) | C15—H15A | 0.98 |
C3—N4 | 1.462 (2) | C15—H15B | 0.98 |
C3—C10 | 1.529 (2) | C15—H15C | 0.98 |
C3—H3 | 0.936 (16) | C16—O9 | 1.435 (2) |
C5—O3 | 1.2309 (19) | C16—C17 | 1.499 (3) |
C5—N4 | 1.360 (2) | C16—H16A | 1.07 (2) |
C5—C6 | 1.525 (2) | C16—H16B | 0.949 (19) |
C6—O4 | 1.4629 (18) | C17—C18 | 1.381 (3) |
C6—C7 | 1.509 (2) | C17—C22 | 1.382 (3) |
C6—H6 | 0.928 (15) | C18—C19 | 1.377 (3) |
C7—O8 | 1.426 (2) | C18—H18 | 0.93 (2) |
C7—C8 | 1.513 (2) | C19—C20 | 1.381 (3) |
C7—H7 | 0.923 (16) | C19—H19 | 0.96 (2) |
C8—O7 | 1.4195 (19) | C20—C21 | 1.362 (3) |
C8—C9 | 1.508 (2) | C20—H20 | 0.93 (2) |
C8—H8 | 0.946 (16) | C21—C22 | 1.378 (3) |
C9—O9 | 1.4187 (18) | C21—H21 | 0.98 (2) |
C9—C9A | 1.526 (2) | C22—H22 | 0.87 (2) |
C9—H9 | 0.992 (16) | C30—C35 | 1.398 (3) |
C9A—N4 | 1.491 (2) | C30—C31 | 1.413 (3) |
C9A—S1 | 1.8249 (17) | C30—C36 | 1.468 (4) |
C9A—H9A | 1.002 (17) | C31—C32 | 1.368 (4) |
C10—O2 | 1.194 (2) | C31—H31 | 0.95 |
C10—O1 | 1.323 (2) | C32—C33 | 1.365 (3) |
C11—O1 | 1.459 (2) | C32—H32 | 0.95 |
C11—H11A | 0.98 | C33—C34 | 1.380 (3) |
C11—H11B | 0.98 | C33—H33 | 0.95 |
C11—H11C | 0.98 | C34—C35 | 1.375 (3) |
C12—S2 | 1.746 (2) | C34—H34 | 0.95 |
C12—H12A | 0.98 | C35—H35 | 0.95 |
C12—H12B | 0.98 | C36—H36A | 0.98 |
C12—H12C | 0.98 | C36—H36B | 0.98 |
C13—O7 | 1.434 (2) | C36—H36C | 0.98 |
C13—O8 | 1.4537 (19) | O4—S2 | 1.5902 (11) |
C13—C14 | 1.500 (2) | O5—S2 | 1.4180 (14) |
C13—C15 | 1.504 (2) | O6—S2 | 1.4265 (13) |
C3—C2—S1 | 103.08 (12) | H14B—C14—H14C | 109.5 |
C3—C2—H2A | 107.9 (10) | C13—C15—H15A | 109.5 |
S1—C2—H2A | 111.2 (10) | C13—C15—H15B | 109.5 |
C3—C2—H2B | 109.9 (10) | H15A—C15—H15B | 109.5 |
S1—C2—H2B | 109.5 (10) | C13—C15—H15C | 109.5 |
H2A—C2—H2B | 114.6 (15) | H15A—C15—H15C | 109.5 |
N4—C3—C2 | 106.19 (14) | H15B—C15—H15C | 109.5 |
N4—C3—C10 | 109.55 (14) | O9—C16—C17 | 107.45 (15) |
C2—C3—C10 | 112.07 (14) | O9—C16—H16A | 108.5 (12) |
N4—C3—H3 | 106.9 (10) | C17—C16—H16A | 108.4 (12) |
C2—C3—H3 | 112.9 (10) | O9—C16—H16B | 103.9 (12) |
C10—C3—H3 | 109.0 (10) | C17—C16—H16B | 112.4 (12) |
O3—C5—N4 | 121.13 (15) | H16A—C16—H16B | 115.8 (18) |
O3—C5—C6 | 118.07 (15) | C18—C17—C22 | 118.20 (18) |
N4—C5—C6 | 120.77 (14) | C18—C17—C16 | 120.85 (18) |
O4—C6—C7 | 108.94 (13) | C22—C17—C16 | 120.92 (19) |
O4—C6—C5 | 109.68 (13) | C19—C18—C17 | 120.7 (2) |
C7—C6—C5 | 113.13 (14) | C19—C18—H18 | 120.0 (13) |
O4—C6—H6 | 107.2 (9) | C17—C18—H18 | 119.3 (13) |
C7—C6—H6 | 111.4 (9) | C18—C19—C20 | 120.0 (2) |
C5—C6—H6 | 106.3 (10) | C18—C19—H19 | 116.6 (12) |
O8—C7—C6 | 112.34 (14) | C20—C19—H19 | 123.3 (12) |
O8—C7—C8 | 102.92 (13) | C21—C20—C19 | 120.0 (2) |
C6—C7—C8 | 114.53 (14) | C21—C20—H20 | 119.6 (14) |
O8—C7—H7 | 108.8 (9) | C19—C20—H20 | 120.4 (14) |
C6—C7—H7 | 107.9 (10) | C20—C21—C22 | 119.9 (2) |
C8—C7—H7 | 110.3 (9) | C20—C21—H21 | 120.6 (15) |
O7—C8—C9 | 113.58 (13) | C22—C21—H21 | 119.5 (15) |
O7—C8—C7 | 101.84 (12) | C21—C22—C17 | 121.2 (2) |
C9—C8—C7 | 114.59 (14) | C21—C22—H22 | 120.5 (14) |
O7—C8—H8 | 108.4 (10) | C17—C22—H22 | 118.2 (14) |
C9—C8—H8 | 107.9 (10) | C35—C30—C31 | 117.8 (2) |
C7—C8—H8 | 110.3 (9) | C35—C30—C36 | 120.9 (2) |
O9—C9—C8 | 113.98 (13) | C31—C30—C36 | 121.3 (2) |
O9—C9—C9A | 108.20 (13) | C32—C31—C30 | 120.3 (2) |
C8—C9—C9A | 108.29 (13) | C32—C31—H31 | 119.8 |
O9—C9—H9 | 110.8 (9) | C30—C31—H31 | 119.8 |
C8—C9—H9 | 108.9 (10) | C33—C32—C31 | 121.8 (3) |
C9A—C9—H9 | 106.4 (9) | C33—C32—H32 | 119.1 |
N4—C9A—C9 | 114.01 (12) | C31—C32—H32 | 119.1 |
N4—C9A—S1 | 105.22 (11) | C32—C33—C34 | 118.4 (3) |
C9—C9A—S1 | 111.06 (11) | C32—C33—H33 | 120.8 |
N4—C9A—H9A | 109.9 (9) | C34—C33—H33 | 120.8 |
C9—C9A—H9A | 109.2 (10) | C35—C34—C33 | 121.9 (2) |
S1—C9A—H9A | 107.2 (9) | C35—C34—H34 | 119 |
O2—C10—O1 | 125.18 (17) | C33—C34—H34 | 119 |
O2—C10—C3 | 124.65 (16) | C34—C35—C30 | 119.8 (2) |
O1—C10—C3 | 110.18 (15) | C34—C35—H35 | 120.1 |
O1—C11—H11A | 109.5 | C30—C35—H35 | 120.1 |
O1—C11—H11B | 109.5 | C30—C36—H36A | 109.5 |
H11A—C11—H11B | 109.5 | C30—C36—H36B | 109.5 |
O1—C11—H11C | 109.5 | H36A—C36—H36B | 109.5 |
H11A—C11—H11C | 109.5 | C30—C36—H36C | 109.5 |
H11B—C11—H11C | 109.5 | H36A—C36—H36C | 109.5 |
S2—C12—H12A | 109.5 | H36B—C36—H36C | 109.5 |
S2—C12—H12B | 109.5 | C5—N4—C3 | 117.25 (14) |
H12A—C12—H12B | 109.5 | C5—N4—C9A | 127.52 (14) |
S2—C12—H12C | 109.5 | C3—N4—C9A | 114.03 (13) |
H12A—C12—H12C | 109.5 | C10—O1—C11 | 117.07 (16) |
H12B—C12—H12C | 109.5 | C6—O4—S2 | 119.52 (10) |
O7—C13—O8 | 105.69 (13) | C8—O7—C13 | 105.45 (11) |
O7—C13—C14 | 107.47 (14) | C7—O8—C13 | 107.76 (12) |
O8—C13—C14 | 110.27 (13) | C9—O9—C16 | 114.29 (13) |
O7—C13—C15 | 110.95 (13) | C2—S1—C9A | 91.98 (8) |
O8—C13—C15 | 107.65 (14) | O5—S2—O6 | 119.70 (9) |
C14—C13—C15 | 114.47 (17) | O5—S2—O4 | 103.95 (7) |
C13—C14—H14A | 109.5 | O6—S2—O4 | 108.94 (7) |
C13—C14—H14B | 109.5 | O5—S2—C12 | 110.77 (10) |
H14A—C14—H14B | 109.5 | O6—S2—C12 | 109.23 (10) |
C13—C14—H14C | 109.5 | O4—S2—C12 | 102.80 (8) |
H14A—C14—H14C | 109.5 | ||
S1—C2—C3—N4 | 44.96 (15) | C32—C33—C34—C35 | 0.2 (4) |
S1—C2—C3—C10 | −74.62 (16) | C33—C34—C35—C30 | −0.3 (3) |
O3—C5—C6—O4 | 109.63 (16) | C31—C30—C35—C34 | −0.1 (3) |
N4—C5—C6—O4 | −72.22 (18) | C36—C30—C35—C34 | −178.2 (2) |
O3—C5—C6—C7 | −128.53 (16) | O3—C5—N4—C3 | −4.1 (2) |
N4—C5—C6—C7 | 49.6 (2) | C6—C5—N4—C3 | 177.82 (14) |
O4—C6—C7—O8 | −72.79 (16) | O3—C5—N4—C9A | −170.73 (15) |
C5—C6—C7—O8 | 164.96 (13) | C6—C5—N4—C9A | 11.2 (2) |
O4—C6—C7—C8 | 44.17 (19) | C2—C3—N4—C5 | 159.54 (14) |
C5—C6—C7—C8 | −78.08 (18) | C10—C3—N4—C5 | −79.24 (18) |
O8—C7—C8—O7 | −37.25 (15) | C2—C3—N4—C9A | −32.03 (18) |
C6—C7—C8—O7 | −159.49 (14) | C10—C3—N4—C9A | 89.18 (16) |
O8—C7—C8—C9 | −160.31 (14) | C9—C9A—N4—C5 | −67.5 (2) |
C6—C7—C8—C9 | 77.46 (18) | S1—C9A—N4—C5 | 170.54 (13) |
O7—C8—C9—O9 | −67.30 (17) | C9—C9A—N4—C3 | 125.47 (15) |
C7—C8—C9—O9 | 49.18 (18) | S1—C9A—N4—C3 | 3.54 (16) |
O7—C8—C9—C9A | 172.24 (13) | O2—C10—O1—C11 | −3.0 (3) |
C7—C8—C9—C9A | −71.28 (17) | C3—C10—O1—C11 | 177.43 (15) |
O9—C9—C9A—N4 | −47.55 (17) | C7—C6—O4—S2 | 134.56 (12) |
C8—C9—C9A—N4 | 76.45 (17) | C5—C6—O4—S2 | −101.13 (13) |
O9—C9—C9A—S1 | 71.10 (14) | C9—C8—O7—C13 | 163.38 (13) |
C8—C9—C9A—S1 | −164.90 (11) | C7—C8—O7—C13 | 39.64 (15) |
N4—C3—C10—O2 | 3.7 (2) | O8—C13—O7—C8 | −27.26 (15) |
C2—C3—C10—O2 | 121.3 (2) | C14—C13—O7—C8 | −145.01 (14) |
N4—C3—C10—O1 | −176.67 (14) | C15—C13—O7—C8 | 89.15 (16) |
C2—C3—C10—O1 | −59.08 (19) | C6—C7—O8—C13 | 144.76 (13) |
O9—C16—C17—C18 | −75.3 (2) | C8—C7—O8—C13 | 21.06 (16) |
O9—C16—C17—C22 | 102.5 (2) | O7—C13—O8—C7 | 2.65 (16) |
C22—C17—C18—C19 | −0.2 (3) | C14—C13—O8—C7 | 118.51 (15) |
C16—C17—C18—C19 | 177.69 (18) | C15—C13—O8—C7 | −115.97 (15) |
C17—C18—C19—C20 | 0.7 (3) | C8—C9—O9—C16 | 89.06 (17) |
C18—C19—C20—C21 | −0.3 (3) | C9A—C9—O9—C16 | −150.42 (15) |
C19—C20—C21—C22 | −0.6 (3) | C17—C16—O9—C9 | 173.04 (15) |
C20—C21—C22—C17 | 1.2 (3) | C3—C2—S1—C9A | −37.91 (13) |
C18—C17—C22—C21 | −0.8 (3) | N4—C9A—S1—C2 | 20.48 (12) |
C16—C17—C22—C21 | −178.62 (18) | C9—C9A—S1—C2 | −103.33 (12) |
C35—C30—C31—C32 | 0.5 (3) | C6—O4—S2—O5 | −163.57 (12) |
C36—C30—C31—C32 | 178.6 (2) | C6—O4—S2—O6 | −34.90 (14) |
C30—C31—C32—C33 | −0.6 (3) | C6—O4—S2—C12 | 80.89 (13) |
C31—C32—C33—C34 | 0.2 (4) |
Experimental details
Crystal data | |
Chemical formula | C21H27NO9S2·C7H8 |
Mr | 593.69 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 193 |
a, b, c (Å) | 10.1251 (6), 11.4082 (5), 25.4972 (15) |
V (Å3) | 2945.2 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.23 |
Crystal size (mm) | 0.4 × 0.4 × 0.05 |
Data collection | |
Diffractometer | Stoe IPDS 2 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 29561, 5724, 4668 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.616 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.049, 0.89 |
No. of reflections | 5724 |
No. of parameters | 426 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.14, −0.18 |
Absolute structure | Flack (1983), with 2479 Friedel pairs |
Absolute structure parameter | 0.02 (4) |
Computer programs: X-AREA (Stoe & Cie, 2005), X-AREA, SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 1997), DIAMOND (Brandenburg, 2004), WinGX (Farrugia, 1999).
C2—C3 | 1.511 (2) | C7—C8 | 1.513 (2) |
C2—S1 | 1.8046 (19) | C8—O7 | 1.4195 (19) |
C3—N4 | 1.462 (2) | C8—C9 | 1.508 (2) |
C5—N4 | 1.360 (2) | C9—C9A | 1.526 (2) |
C5—C6 | 1.525 (2) | C9A—N4 | 1.491 (2) |
C6—C7 | 1.509 (2) | C9A—S1 | 1.8249 (17) |
C7—O8 | 1.426 (2) | ||
C3—C2—S1 | 103.08 (12) | N4—C9A—C9 | 114.01 (12) |
N4—C3—C2 | 106.19 (14) | N4—C9A—S1 | 105.22 (11) |
N4—C5—C6 | 120.77 (14) | C9—C9A—S1 | 111.06 (11) |
C7—C6—C5 | 113.13 (14) | O7—C13—O8 | 105.69 (13) |
O8—C7—C6 | 112.34 (14) | C5—N4—C3 | 117.25 (14) |
O8—C7—C8 | 102.92 (13) | C5—N4—C9A | 127.52 (14) |
C6—C7—C8 | 114.53 (14) | C3—N4—C9A | 114.03 (13) |
O7—C8—C9 | 113.58 (13) | C8—O7—C13 | 105.45 (11) |
O7—C8—C7 | 101.84 (12) | C7—O8—C13 | 107.76 (12) |
C9—C8—C7 | 114.59 (14) | C2—S1—C9A | 91.98 (8) |
C8—C9—C9A | 108.29 (13) | ||
S1—C2—C3—N4 | 44.96 (15) | C2—C3—N4—C5 | 159.54 (14) |
N4—C5—C6—C7 | 49.6 (2) | C2—C3—N4—C9A | −32.03 (18) |
C5—C6—C7—O8 | 164.96 (13) | C9—C9A—N4—C5 | −67.5 (2) |
C5—C6—C7—C8 | −78.08 (18) | S1—C9A—N4—C5 | 170.54 (13) |
O8—C7—C8—O7 | −37.25 (15) | C9—C9A—N4—C3 | 125.47 (15) |
C6—C7—C8—O7 | −159.49 (14) | S1—C9A—N4—C3 | 3.54 (16) |
O8—C7—C8—C9 | −160.31 (14) | C9—C8—O7—C13 | 163.38 (13) |
C6—C7—C8—C9 | 77.46 (18) | C7—C8—O7—C13 | 39.64 (15) |
O7—C8—C9—O9 | −67.30 (17) | O8—C13—O7—C8 | −27.26 (15) |
O7—C8—C9—C9A | 172.24 (13) | C6—C7—O8—C13 | 144.76 (13) |
C7—C8—C9—C9A | −71.28 (17) | C8—C7—O8—C13 | 21.06 (16) |
C8—C9—C9A—N4 | 76.45 (17) | O7—C13—O8—C7 | 2.65 (16) |
C8—C9—C9A—S1 | −164.90 (11) | C3—C2—S1—C9A | −37.91 (13) |
C6—C5—N4—C3 | 177.82 (14) | N4—C9A—S1—C2 | 20.48 (12) |
C6—C5—N4—C9A | 11.2 (2) | C9—C9A—S1—C2 | −103.33 (12) |
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Bicyclic dipeptide mimetics can induce and stabilize hairpin turns in peptide strands (Nagai & Sato, 1985). The originally proposed mechanism has been challenged by recent X-ray and NMR studies (Tremmel & Geyer, 2004). Polyhydroxylated 7,5-fused bicyclic thiazolidinlactams have been inserted into both cyclic and linear oligopeptids (Tremmel & Geyer, 2002). The present ester molecule of the title compound, (I), is a precurser for a class of carbohydrate-based dipeptide derivatives. The mesyl group can be exchanged for an azido group and subsequent reduction forms the amino group of the dipeptide mimetic. After cleavage of the isopropylidene and methylester protecting groups, a hydrophilic bicyclic dipeptide mimetic with an aromatic side chain is obtained. It can serve as a rigid substituent of a D-Phe-Pro dipeptide.
The starting reaction for the synthesis of the mesylated 7,5-fused bicyclic thiazolidinlactam, (I) (Fig. 1), is the condensation of D-γ-mannuronolactone with the methyl ester of L-cysteine. After protection of two hydroxy groups with 2,2-dimethoxypropane, the alcohol in position 9 is selectively activated with mesylchloride. Finally, the benzylation of the remaining free hydroxyl group is performed with benzylbromide and sodium hydride.
In both the crystalline state and in solution the seven-membered lactam ring of (I) populates an inverted chair conformation, compared with the gluco derivatives (Geyer et al., 1999).