Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S160053680702692X/lh2404sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S160053680702692X/lh2404Isup2.hkl |
CCDC reference: 654872
Key indicators
- Single-crystal X-ray study
- T = 293 K
- Mean (C-C) = 0.005 Å
- R factor = 0.048
- wR factor = 0.123
- Data-to-parameter ratio = 9.5
checkCIF/PLATON results
No syntax errors found
Alert level A PLAT242_ALERT_2_A Check Low Ueq as Compared to Neighbors for C9
Author Response: This may be result of marginal disorder but it has not been modelled. |
Alert level B PLAT220_ALERT_2_B Large Non-Solvent C Ueq(max)/Ueq(min) ... 3.84 Ratio PLAT222_ALERT_3_B Large Non-Solvent H Ueq(max)/Ueq(min) ... 4.78 Ratio PLAT241_ALERT_2_B Check High Ueq as Compared to Neighbors for O3
Alert level C PLAT048_ALERT_1_C MoietyFormula Not Given ........................ ? PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT153_ALERT_1_C The su's on the Cell Axes are Equal (x 100000) 400 Ang. PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for O4 PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C17 PLAT340_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 5 PLAT731_ALERT_1_C Bond Calc 0.81(4), Rep 0.806(19) ...... 2.11 su-Ra O2 -H2X 1.555 1.555 PLAT735_ALERT_1_C D-H Calc 0.81(4), Rep 0.806(19) ...... 2.11 su-Ra O2 -H2X 1.555 1.555
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 27.12 From the CIF: _reflns_number_total 2466 Count of symmetry unique reflns 2504 Completeness (_total/calc) 98.48% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 0 Fraction of Friedel pairs measured 0.000 Are heavy atom types Z>Si present no PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature 293 K PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature . 293 K PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3 = . S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C4 = . S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C5 = . S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C7 = . R PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 2
1 ALERT level A = In general: serious problem 3 ALERT level B = Potentially serious problem 8 ALERT level C = Check and explain 8 ALERT level G = General alerts; check 11 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 5 ALERT type 2 Indicator that the structure model may be wrong or deficient 3 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check
The literature procedure according to Sarko et al. (1996) was followed. To a cold (195k) solution of (3S,4S)-3-acetyl-1-benzhydryl -4-((R)-2,2-dimethyl-1,3-dioxolan-4-yl)-2-azetidinone (1.0 mmol) in 10 mL of CH2Cl2, was added TiCl4 (110µl, 1.0 mmol) with vigrous stirring under Argon atomsphere. After 10 min, pyr·BH 3 (140µl, 1.0 mmol) was slowly added. The reaction was quenched with 1 N HCl (2 ml) after 15 min, and the reaction mixture was warmed to r.t., the organic layer was separated and washed with brine, dried over anhyd. MgSO4, and concentrated in vacuo, Chromatography gave the title compound 28 mg (73%), m.p. 415 K. Full spectroscopic and physical characterization will be reported elsewhere.
In the absence of significant anomalous dispersion effects Fridel pairs were merged. All H atoms were placed in geometrically idealized position and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.98 Å and with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms. Methyl groups were allowed to rotate freely about the C—C bond. The H atom bonded to O was isotropically refined with a distance restraint of O—H = 0.80 (6) Å. Atoms C10/C11/O3/O4 have larger than normal anistropic displacement parameters and this may be due to marginal disorder in this part of the molecule. This was not modelled.
During our study on the synthesis of carbapenems, a class of antibiotics with pronounced broad-spectrum antibacterial activity, (Kawabata et al., 1988), the title compound was produced and is a key intermediate in our newly designed synthetic route to carbapenems. The title compound was synthesized through the reduction of (3S,4S)-3-acetyl-1-benzhydryl-4-((R)-2,2-dimethyl- 1,3-dioxolan-4-yl)-2-azetidinone from L-ascorbic acid. The absolute configuration was difficult to determined by other analytical methods due to the free rotation of C3—C5 single bond. Here we report the crystal structure of the title compound.
Fig. 1 shows the molecular structrue of the title compound. The enantiomer was selected on the basis of the configuration of the starting material. All chiral carbon atoms are S-configuration except C7. The 4-membered ring is almost a planar with a dihedral of 1.2 (2)° for N1—C2—C3—C4, In the 5-membered ring, the dihedral of C9—O4—C7—C8 is 3.4 (4)°, and the dihedral angle of C9/O3/C8/C7 is -18.6 (5)°. The C9—C10 and C9—C11 bond lengths are shorter than the typical Csp3—Csp3 bond distance, possibly as a result of marginal disorder in this area.
For background information, see: Kawabata et al. (1988). For the synthetic procedure, see: Sarko et al. (1996).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 2000); software used to prepare material for publication: SHELXTL.
C23H27NO4 | F(000) = 408 |
Mr = 381.46 | Dx = 1.188 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 769 reflections |
a = 10.720 (4) Å | θ = 2.7–23.4° |
b = 9.192 (4) Å | µ = 0.08 mm−1 |
c = 10.819 (4) Å | T = 293 K |
β = 90.890 (5)° | Block, colorless |
V = 1065.9 (7) Å3 | 0.15 × 0.15 × 0.12 mm |
Z = 2 |
Bruker SMART APEX CCD area-detector diffractometer | 2466 independent reflections |
Radiation source: fine-focus sealed tube | 1973 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.026 |
φ and ω scans | θmax = 27.1°, θmin = 1.9° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→13 |
Tmin = 0.988, Tmax = 0.990 | k = −8→11 |
5246 measured reflections | l = −13→13 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.048 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.123 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0578P)2 + 0.1569P] where P = (Fo2 + 2Fc2)/3 |
2466 reflections | (Δ/σ)max < 0.001 |
260 parameters | Δρmax = 0.19 e Å−3 |
2 restraints | Δρmin = −0.13 e Å−3 |
C23H27NO4 | V = 1065.9 (7) Å3 |
Mr = 381.46 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.720 (4) Å | µ = 0.08 mm−1 |
b = 9.192 (4) Å | T = 293 K |
c = 10.819 (4) Å | 0.15 × 0.15 × 0.12 mm |
β = 90.890 (5)° |
Bruker SMART APEX CCD area-detector diffractometer | 2466 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1973 reflections with I > 2σ(I) |
Tmin = 0.988, Tmax = 0.990 | Rint = 0.026 |
5246 measured reflections |
R[F2 > 2σ(F2)] = 0.048 | 2 restraints |
wR(F2) = 0.123 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.19 e Å−3 |
2466 reflections | Δρmin = −0.13 e Å−3 |
260 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 | 0.2959 (2) | 0.5939 (3) | 0.5357 (2) | 0.0796 (8) | |
O2 | 0.5052 (3) | 0.1621 (3) | 0.6167 (2) | 0.0893 (9) | |
H2X | 0.566 (3) | 0.135 (6) | 0.580 (4) | 0.111 (17)* | |
O3 | 0.4631 (3) | 0.2094 (4) | 1.0163 (3) | 0.1206 (14) | |
O4 | 0.3240 (2) | 0.3847 (4) | 0.98493 (18) | 0.0871 (9) | |
N1 | 0.25812 (18) | 0.4805 (3) | 0.72615 (19) | 0.0455 (5) | |
C2 | 0.3178 (2) | 0.5096 (3) | 0.6201 (3) | 0.0535 (7) | |
C3 | 0.4185 (2) | 0.3955 (3) | 0.6467 (2) | 0.0508 (7) | |
H3 | 0.4985 | 0.4420 | 0.6668 | 0.061* | |
C4 | 0.3440 (2) | 0.3646 (3) | 0.7658 (2) | 0.0425 (5) | |
H4 | 0.3043 | 0.2685 | 0.7643 | 0.051* | |
C5 | 0.4357 (3) | 0.2721 (4) | 0.5551 (3) | 0.0673 (9) | |
H5 | 0.4845 | 0.3082 | 0.4857 | 0.081* | |
C6 | 0.3138 (4) | 0.2112 (6) | 0.5050 (4) | 0.0938 (14) | |
H6A | 0.3305 | 0.1295 | 0.4525 | 0.141* | |
H6B | 0.2707 | 0.2849 | 0.4583 | 0.141* | |
H6C | 0.2629 | 0.1805 | 0.5725 | 0.141* | |
C7 | 0.4106 (3) | 0.3944 (4) | 0.8868 (2) | 0.0559 (7) | |
H7 | 0.4479 | 0.4917 | 0.8853 | 0.067* | |
C8 | 0.5090 (3) | 0.2823 (5) | 0.9209 (3) | 0.0751 (11) | |
H8A | 0.5238 | 0.2174 | 0.8520 | 0.090* | |
H8B | 0.5869 | 0.3295 | 0.9440 | 0.090* | |
C9 | 0.3664 (3) | 0.2851 (4) | 1.0748 (3) | 0.0676 (8) | |
C10 | 0.2653 (6) | 0.1807 (9) | 1.1042 (6) | 0.163 (3) | |
H10A | 0.1959 | 0.2325 | 1.1380 | 0.244* | |
H10B | 0.2957 | 0.1110 | 1.1635 | 0.244* | |
H10C | 0.2389 | 0.1312 | 1.0302 | 0.244* | |
C11 | 0.4124 (6) | 0.3664 (8) | 1.1846 (4) | 0.127 (2) | |
H11A | 0.4768 | 0.4328 | 1.1604 | 0.190* | |
H11B | 0.4455 | 0.2993 | 1.2447 | 0.190* | |
H11C | 0.3448 | 0.4200 | 1.2199 | 0.190* | |
C12 | 0.1470 (2) | 0.5359 (3) | 0.7899 (2) | 0.0450 (6) | |
H12 | 0.1652 | 0.5270 | 0.8786 | 0.054* | |
C13 | 0.1287 (3) | 0.6983 (3) | 0.7648 (3) | 0.0496 (6) | |
C14 | 0.0195 (3) | 0.7568 (4) | 0.7190 (3) | 0.0618 (8) | |
H14 | −0.0455 | 0.6958 | 0.6947 | 0.074* | |
C15 | 0.0056 (3) | 0.9070 (4) | 0.7088 (4) | 0.0747 (10) | |
H15 | −0.0689 | 0.9453 | 0.6779 | 0.090* | |
C16 | 0.0989 (4) | 0.9976 (4) | 0.7433 (4) | 0.0877 (12) | |
H16 | 0.0888 | 1.0979 | 0.7371 | 0.105* | |
C17 | 0.2092 (4) | 0.9395 (4) | 0.7879 (5) | 0.1029 (16) | |
H17 | 0.2743 | 1.0009 | 0.8113 | 0.123* | |
C18 | 0.2237 (3) | 0.7912 (4) | 0.7980 (4) | 0.0837 (12) | |
H18 | 0.2988 | 0.7535 | 0.8277 | 0.100* | |
C19 | 0.0345 (2) | 0.4398 (3) | 0.7639 (2) | 0.0453 (6) | |
C20 | −0.0062 (3) | 0.4086 (4) | 0.6451 (3) | 0.0656 (8) | |
H20 | 0.0368 | 0.4464 | 0.5784 | 0.079* | |
C21 | −0.1091 (3) | 0.3227 (5) | 0.6239 (4) | 0.0798 (11) | |
H21 | −0.1352 | 0.3028 | 0.5433 | 0.096* | |
C22 | −0.1727 (3) | 0.2669 (5) | 0.7205 (4) | 0.0815 (11) | |
H22 | −0.2433 | 0.2106 | 0.7053 | 0.098* | |
C23 | −0.1347 (3) | 0.2920 (5) | 0.8398 (4) | 0.0797 (10) | |
H23 | −0.1772 | 0.2504 | 0.9053 | 0.096* | |
C24 | −0.0301 (3) | 0.3819 (4) | 0.8620 (3) | 0.0610 (7) | |
H24 | −0.0045 | 0.4023 | 0.9427 | 0.073* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0720 (14) | 0.0947 (19) | 0.0724 (15) | 0.0133 (14) | 0.0149 (11) | 0.0440 (15) |
O2 | 0.0973 (19) | 0.100 (2) | 0.0714 (15) | 0.0469 (17) | 0.0206 (14) | 0.0062 (15) |
O3 | 0.136 (3) | 0.104 (2) | 0.124 (2) | 0.064 (2) | 0.066 (2) | 0.058 (2) |
O4 | 0.0758 (14) | 0.140 (3) | 0.0460 (11) | 0.0508 (17) | 0.0084 (10) | 0.0085 (14) |
N1 | 0.0405 (10) | 0.0474 (13) | 0.0487 (11) | 0.0027 (10) | 0.0049 (8) | 0.0084 (10) |
C2 | 0.0450 (13) | 0.0583 (18) | 0.0573 (16) | 0.0002 (13) | 0.0058 (11) | 0.0156 (15) |
C3 | 0.0385 (12) | 0.0630 (18) | 0.0512 (14) | 0.0037 (12) | 0.0094 (10) | 0.0127 (14) |
C4 | 0.0426 (12) | 0.0394 (13) | 0.0457 (13) | 0.0022 (11) | 0.0069 (10) | 0.0031 (11) |
C5 | 0.0659 (17) | 0.089 (2) | 0.0475 (15) | 0.0158 (19) | 0.0178 (13) | 0.0044 (17) |
C6 | 0.093 (3) | 0.118 (4) | 0.070 (2) | 0.008 (3) | 0.001 (2) | −0.030 (2) |
C7 | 0.0565 (15) | 0.0640 (19) | 0.0471 (14) | 0.0067 (14) | 0.0006 (11) | −0.0025 (14) |
C8 | 0.0577 (17) | 0.112 (3) | 0.0558 (17) | 0.029 (2) | −0.0008 (14) | 0.009 (2) |
C9 | 0.0714 (18) | 0.070 (2) | 0.0620 (18) | 0.0051 (18) | 0.0129 (15) | 0.0057 (17) |
C10 | 0.177 (6) | 0.143 (6) | 0.172 (6) | −0.071 (5) | 0.089 (5) | −0.030 (5) |
C11 | 0.157 (4) | 0.152 (5) | 0.070 (2) | 0.012 (5) | −0.035 (3) | −0.009 (3) |
C12 | 0.0435 (13) | 0.0476 (15) | 0.0440 (13) | 0.0034 (11) | 0.0046 (10) | 0.0008 (11) |
C13 | 0.0460 (14) | 0.0447 (15) | 0.0583 (16) | 0.0007 (12) | 0.0049 (12) | −0.0006 (13) |
C14 | 0.0498 (16) | 0.0489 (17) | 0.087 (2) | 0.0037 (13) | 0.0058 (15) | −0.0006 (16) |
C15 | 0.0621 (18) | 0.054 (2) | 0.108 (3) | 0.0180 (16) | 0.0096 (18) | 0.0102 (19) |
C16 | 0.085 (3) | 0.0405 (17) | 0.138 (4) | 0.0032 (18) | 0.012 (2) | 0.003 (2) |
C17 | 0.085 (3) | 0.051 (2) | 0.172 (5) | −0.012 (2) | −0.022 (3) | −0.009 (3) |
C18 | 0.069 (2) | 0.050 (2) | 0.131 (3) | −0.0026 (17) | −0.026 (2) | 0.001 (2) |
C19 | 0.0368 (12) | 0.0401 (14) | 0.0592 (15) | 0.0045 (10) | 0.0031 (11) | −0.0009 (12) |
C20 | 0.0621 (17) | 0.068 (2) | 0.0663 (18) | −0.0026 (16) | 0.0014 (14) | −0.0035 (17) |
C21 | 0.067 (2) | 0.079 (3) | 0.093 (2) | −0.0069 (19) | −0.0119 (18) | −0.021 (2) |
C22 | 0.0520 (17) | 0.068 (2) | 0.124 (3) | −0.0136 (18) | 0.0027 (19) | −0.013 (2) |
C23 | 0.0549 (17) | 0.077 (2) | 0.108 (3) | −0.0097 (18) | 0.0213 (18) | 0.005 (2) |
C24 | 0.0544 (15) | 0.0589 (18) | 0.0700 (17) | 0.0027 (15) | 0.0117 (13) | 0.0000 (16) |
O1—C2 | 1.218 (4) | C10—H10C | 0.9599 |
O2—C5 | 1.416 (4) | C11—H11A | 0.9599 |
O2—H2X | 0.806 (19) | C11—H11B | 0.9599 |
O3—C8 | 1.331 (4) | C11—H11C | 0.9599 |
O3—C9 | 1.408 (4) | C12—C19 | 1.518 (4) |
O4—C9 | 1.405 (4) | C12—C13 | 1.529 (4) |
O4—C7 | 1.424 (4) | C12—H12 | 0.9800 |
N1—C2 | 1.349 (3) | C13—C18 | 1.373 (5) |
N1—C4 | 1.468 (3) | C13—C14 | 1.374 (4) |
N1—C12 | 1.476 (3) | C14—C15 | 1.393 (5) |
C2—C3 | 1.529 (4) | C14—H14 | 0.9300 |
C3—C5 | 1.519 (5) | C15—C16 | 1.349 (5) |
C3—C4 | 1.553 (3) | C15—H15 | 0.9300 |
C3—H3 | 0.9800 | C16—C17 | 1.378 (6) |
C4—C7 | 1.506 (4) | C16—H16 | 0.9300 |
C4—H4 | 0.9800 | C17—C18 | 1.376 (6) |
C5—C6 | 1.515 (5) | C17—H17 | 0.9300 |
C5—H5 | 0.9800 | C18—H18 | 0.9300 |
C6—H6A | 0.9599 | C19—C20 | 1.381 (4) |
C6—H6B | 0.9599 | C19—C24 | 1.383 (4) |
C6—H6C | 0.9599 | C20—C21 | 1.373 (5) |
C7—C8 | 1.517 (4) | C20—H20 | 0.9300 |
C7—H7 | 0.9800 | C21—C22 | 1.357 (6) |
C8—H8A | 0.9700 | C21—H21 | 0.9300 |
C8—H8B | 0.9700 | C22—C23 | 1.367 (5) |
C9—C11 | 1.482 (6) | C22—H22 | 0.9300 |
C9—C10 | 1.486 (6) | C23—C24 | 1.411 (5) |
C10—H10A | 0.9599 | C23—H23 | 0.9300 |
C10—H10B | 0.9599 | C24—H24 | 0.9300 |
C5—O2—H2X | 114 (4) | H10A—C10—H10B | 109.5 |
C8—O3—C9 | 112.5 (3) | C9—C10—H10C | 109.5 |
C9—O4—C7 | 110.5 (2) | H10A—C10—H10C | 109.5 |
C2—N1—C4 | 95.11 (19) | H10B—C10—H10C | 109.5 |
C2—N1—C12 | 136.5 (2) | C9—C11—H11A | 109.5 |
C4—N1—C12 | 128.4 (2) | C9—C11—H11B | 109.5 |
O1—C2—N1 | 132.5 (3) | H11A—C11—H11B | 109.5 |
O1—C2—C3 | 134.8 (3) | C9—C11—H11C | 109.5 |
N1—C2—C3 | 92.7 (2) | H11A—C11—H11C | 109.5 |
C5—C3—C2 | 118.8 (2) | H11B—C11—H11C | 109.5 |
C5—C3—C4 | 118.3 (3) | N1—C12—C19 | 110.9 (2) |
C2—C3—C4 | 84.89 (18) | N1—C12—C13 | 110.9 (2) |
C5—C3—H3 | 110.8 | C19—C12—C13 | 115.8 (2) |
C2—C3—H3 | 110.8 | N1—C12—H12 | 106.2 |
C4—C3—H3 | 110.8 | C19—C12—H12 | 106.2 |
N1—C4—C7 | 114.1 (2) | C13—C12—H12 | 106.2 |
N1—C4—C3 | 87.29 (18) | C18—C13—C14 | 118.3 (3) |
C7—C4—C3 | 116.4 (2) | C18—C13—C12 | 117.9 (3) |
N1—C4—H4 | 112.3 | C14—C13—C12 | 123.6 (3) |
C7—C4—H4 | 112.3 | C13—C14—C15 | 120.4 (3) |
C3—C4—H4 | 112.3 | C13—C14—H14 | 119.8 |
O2—C5—C6 | 110.5 (4) | C15—C14—H14 | 119.8 |
O2—C5—C3 | 107.1 (2) | C16—C15—C14 | 120.8 (3) |
C6—C5—C3 | 113.4 (3) | C16—C15—H15 | 119.6 |
O2—C5—H5 | 108.6 | C14—C15—H15 | 119.6 |
C6—C5—H5 | 108.6 | C15—C16—C17 | 119.1 (3) |
C3—C5—H5 | 108.6 | C15—C16—H16 | 120.5 |
C5—C6—H6A | 109.5 | C17—C16—H16 | 120.5 |
C5—C6—H6B | 109.5 | C18—C17—C16 | 120.5 (4) |
H6A—C6—H6B | 109.5 | C18—C17—H17 | 119.8 |
C5—C6—H6C | 109.5 | C16—C17—H17 | 119.8 |
H6A—C6—H6C | 109.5 | C13—C18—C17 | 120.9 (4) |
H6B—C6—H6C | 109.5 | C13—C18—H18 | 119.6 |
O4—C7—C4 | 109.3 (2) | C17—C18—H18 | 119.6 |
O4—C7—C8 | 103.6 (2) | C20—C19—C24 | 118.7 (3) |
C4—C7—C8 | 114.0 (3) | C20—C19—C12 | 122.1 (3) |
O4—C7—H7 | 109.9 | C24—C19—C12 | 119.2 (2) |
C4—C7—H7 | 109.9 | C21—C20—C19 | 121.1 (3) |
C8—C7—H7 | 109.9 | C21—C20—H20 | 119.5 |
O3—C8—C7 | 105.5 (2) | C19—C20—H20 | 119.5 |
O3—C8—H8A | 110.6 | C22—C21—C20 | 120.1 (3) |
C7—C8—H8A | 110.6 | C22—C21—H21 | 120.0 |
O3—C8—H8B | 110.6 | C20—C21—H21 | 120.0 |
C7—C8—H8B | 110.6 | C21—C22—C23 | 121.1 (3) |
H8A—C8—H8B | 108.8 | C21—C22—H22 | 119.4 |
O4—C9—O3 | 104.1 (2) | C23—C22—H22 | 119.4 |
O4—C9—C11 | 109.0 (4) | C22—C23—C24 | 118.9 (3) |
O3—C9—C11 | 111.8 (4) | C22—C23—H23 | 120.5 |
O4—C9—C10 | 109.9 (4) | C24—C23—H23 | 120.5 |
O3—C9—C10 | 108.8 (4) | C19—C24—C23 | 120.0 (3) |
C11—C9—C10 | 112.9 (4) | C19—C24—H24 | 120.0 |
C9—C10—H10A | 109.5 | C23—C24—H24 | 120.0 |
C9—C10—H10B | 109.5 | ||
C4—N1—C2—O1 | 177.6 (4) | C8—O3—C9—O4 | 20.7 (5) |
C12—N1—C2—O1 | −2.4 (6) | C8—O3—C9—C11 | −96.9 (5) |
C4—N1—C2—C3 | −1.3 (2) | C8—O3—C9—C10 | 137.8 (5) |
C12—N1—C2—C3 | 178.8 (3) | C2—N1—C12—C19 | 97.6 (4) |
O1—C2—C3—C5 | −58.0 (5) | C4—N1—C12—C19 | −82.4 (3) |
N1—C2—C3—C5 | 120.8 (3) | C2—N1—C12—C13 | −32.6 (4) |
O1—C2—C3—C4 | −177.6 (4) | C4—N1—C12—C13 | 147.4 (3) |
N1—C2—C3—C4 | 1.2 (2) | N1—C12—C13—C18 | −58.6 (4) |
C2—N1—C4—C7 | 119.1 (2) | C19—C12—C13—C18 | 173.9 (3) |
C12—N1—C4—C7 | −61.0 (3) | N1—C12—C13—C14 | 126.2 (3) |
C2—N1—C4—C3 | 1.2 (2) | C19—C12—C13—C14 | −1.4 (4) |
C12—N1—C4—C3 | −178.8 (3) | C18—C13—C14—C15 | −1.0 (5) |
C5—C3—C4—N1 | −121.2 (2) | C12—C13—C14—C15 | 174.2 (3) |
C2—C3—C4—N1 | −1.1 (2) | C13—C14—C15—C16 | 0.2 (6) |
C5—C3—C4—C7 | 123.1 (3) | C14—C15—C16—C17 | 0.6 (7) |
C2—C3—C4—C7 | −116.8 (3) | C15—C16—C17—C18 | −0.5 (8) |
C2—C3—C5—O2 | −163.1 (3) | C14—C13—C18—C17 | 1.2 (7) |
C4—C3—C5—O2 | −62.6 (3) | C12—C13—C18—C17 | −174.3 (5) |
C2—C3—C5—C6 | −40.9 (4) | C16—C17—C18—C13 | −0.4 (9) |
C4—C3—C5—C6 | 59.5 (4) | N1—C12—C19—C20 | −55.3 (3) |
C9—O4—C7—C4 | 125.3 (3) | C13—C12—C19—C20 | 72.3 (3) |
C9—O4—C7—C8 | 3.4 (4) | N1—C12—C19—C24 | 125.1 (3) |
N1—C4—C7—O4 | 70.7 (3) | C13—C12—C19—C24 | −107.4 (3) |
C3—C4—C7—O4 | 170.2 (3) | C24—C19—C20—C21 | 0.4 (5) |
N1—C4—C7—C8 | −173.9 (2) | C12—C19—C20—C21 | −179.2 (3) |
C3—C4—C7—C8 | −74.5 (3) | C19—C20—C21—C22 | 0.0 (6) |
C9—O3—C8—C7 | −18.6 (5) | C20—C21—C22—C23 | −1.4 (6) |
O4—C7—C8—O3 | 9.0 (4) | C21—C22—C23—C24 | 2.3 (6) |
C4—C7—C8—O3 | −109.7 (4) | C20—C19—C24—C23 | 0.5 (5) |
C7—O4—C9—O3 | −13.8 (4) | C12—C19—C24—C23 | −179.8 (3) |
C7—O4—C9—C11 | 105.7 (4) | C22—C23—C24—C19 | −1.8 (5) |
C7—O4—C9—C10 | −130.1 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···O4 | 0.98 | 2.42 | 3.141 (3) | 130 |
O2—H2X···O1i | 0.81 (2) | 1.99 (2) | 2.787 (4) | 170 (5) |
C7—H7···O3ii | 0.98 | 2.45 | 3.357 (4) | 153 |
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) −x+1, y+1/2, −z+2. |
Experimental details
Crystal data | |
Chemical formula | C23H27NO4 |
Mr | 381.46 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 10.720 (4), 9.192 (4), 10.819 (4) |
β (°) | 90.890 (5) |
V (Å3) | 1065.9 (7) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.15 × 0.15 × 0.12 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.988, 0.990 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5246, 2466, 1973 |
Rint | 0.026 |
(sin θ/λ)max (Å−1) | 0.641 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.123, 1.02 |
No. of reflections | 2466 |
No. of parameters | 260 |
No. of restraints | 2 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.19, −0.13 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 2000), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
C12—H12···O4 | 0.98 | 2.42 | 3.141 (3) | 129.6 |
O2—H2X···O1i | 0.806 (19) | 1.99 (2) | 2.787 (4) | 170 (5) |
C7—H7···O3ii | 0.98 | 2.45 | 3.357 (4) | 153.3 |
Symmetry codes: (i) −x+1, y−1/2, −z+1; (ii) −x+1, y+1/2, −z+2. |
During our study on the synthesis of carbapenems, a class of antibiotics with pronounced broad-spectrum antibacterial activity, (Kawabata et al., 1988), the title compound was produced and is a key intermediate in our newly designed synthetic route to carbapenems. The title compound was synthesized through the reduction of (3S,4S)-3-acetyl-1-benzhydryl-4-((R)-2,2-dimethyl- 1,3-dioxolan-4-yl)-2-azetidinone from L-ascorbic acid. The absolute configuration was difficult to determined by other analytical methods due to the free rotation of C3—C5 single bond. Here we report the crystal structure of the title compound.
Fig. 1 shows the molecular structrue of the title compound. The enantiomer was selected on the basis of the configuration of the starting material. All chiral carbon atoms are S-configuration except C7. The 4-membered ring is almost a planar with a dihedral of 1.2 (2)° for N1—C2—C3—C4, In the 5-membered ring, the dihedral of C9—O4—C7—C8 is 3.4 (4)°, and the dihedral angle of C9/O3/C8/C7 is -18.6 (5)°. The C9—C10 and C9—C11 bond lengths are shorter than the typical Csp3—Csp3 bond distance, possibly as a result of marginal disorder in this area.