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
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.