Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807038731/bi2220sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807038731/bi2220Isup2.hkl |
CCDC reference: 663676
Key indicators
- Single-crystal X-ray study
- T = 296 K
- Mean (C-C) = 0.004 Å
- R factor = 0.034
- wR factor = 0.087
- Data-to-parameter ratio = 8.6
checkCIF/PLATON results
No syntax errors found
Alert level C PLAT066_ALERT_1_C Predicted and Reported Transmissions Identical . ? PLAT220_ALERT_2_C Large Non-Solvent C Ueq(max)/Ueq(min) ... 2.81 Ratio PLAT222_ALERT_3_C Large Non-Solvent H Ueq(max)/Ueq(min) ... 3.22 Ratio PLAT432_ALERT_2_C Short Inter X...Y Contact O2 .. C12 .. 2.99 Ang.
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 27.50 From the CIF: _reflns_number_total 2612 Count of symmetry unique reflns 2657 Completeness (_total/calc) 98.31% 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 PLAT791_ALERT_1_G Confirm the Absolute Configuration of C3 = . S PLAT791_ALERT_1_G Confirm the Absolute Configuration of C17 = . S PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 4 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 2 ALERT type 2 Indicator that the structure model may be wrong or deficient 2 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 (S)-isocyanate 2 (2.0 mmol) was added to a mixture of alcohol 1 (1.0 mmol) and reagent grade CuCl (0.2 mmol) in dry CH2Cl2 (12 ml) at room temperature (Scheme 2; Duggan & Imagire, 1989). After stirring for 12 h, the reaction mixture was filtered and the filtrate was diluted with CH2Cl2 (20 ml), washed with H2O (20 ml) and brine (20 ml), dried over MgSO4 and concentrated. The crude product (0.43 g, 94%) was recrystallized from 2-propanol (31 ml) to yield a white powder (m.p. 485 K). Crystals suitable for X-ray analysis were obtained from ethyl acetate.
All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances in the range 0.93–0.98 Å and N—H = 0.88 Å, and with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms. The methyl groups were allowed to rotate about their local threefold axes. In the absence of significant anomalous scattering effects, Friedel pairs have been merged as equivalent data. The absolute structure was assigned on the basis of the unchanging chiral centre C17, originating from the isocyanate reactant.
The method for resolution of a tertiary alcohol using a chiral isocyanate reagent has been widely applied (Gibbs et al., 1989). The title compound is a key intermediate in the resolution process of alcohol 1 using the (S)-isocyanate 2 (Scheme 2).
On the basis of the unchanging S configuration of C17, the molecular structure (Figure 1) indicates that the chiral C atom C3 adopts an S configuration. The six-membered lactone ring is twisted with an O1/C2/C3/C4 torsion angle of -21.4 (3) °. The pyrrole ring is also twisted, with a N1/C6/C7/C8 torsion angle of 22.3 (2) °. N—H···O hydrogen bonds exist between molecules, linking them into chains along the c axis.
For related literature, see: Duggan & Imagire (1989); Gibbs et al. (1989).
Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); 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, 1997); software used to prepare material for publication: SHELXTL.
C24H26N2O7 | F(000) = 480 |
Mr = 454.47 | Dx = 1.352 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2yb | Cell parameters from 2722 reflections |
a = 7.3998 (10) Å | θ = 2.2–25.4° |
b = 16.383 (2) Å | µ = 0.10 mm−1 |
c = 9.2162 (13) Å | T = 296 K |
β = 92.322 (2)° | Prism, colourless |
V = 1116.4 (3) Å3 | 0.30 × 0.25 × 0.20 mm |
Z = 2 |
Bruker SMART APEX II CCD diffractometer | 2612 independent reflections |
Radiation source: fine-focus sealed tube | 2352 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.023 |
φ and ω scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −8→9 |
Tmin = 0.971, Tmax = 0.980 | k = −18→21 |
7148 measured reflections | l = −9→11 |
Refinement on F2 | Hydrogen site location: inferred from neighbouring sites |
Least-squares matrix: full | H-atom parameters constrained |
R[F2 > 2σ(F2)] = 0.034 | w = 1/[σ2(Fo2) + (0.0485P)2 + 0.0587P] where P = (Fo2 + 2Fc2)/3 |
wR(F2) = 0.087 | (Δ/σ)max < 0.001 |
S = 1.06 | Δρmax = 0.21 e Å−3 |
2612 reflections | Δρmin = −0.13 e Å−3 |
302 parameters | Extinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
1 restraint | Extinction coefficient: 0.015 (3) |
Primary atom site location: structure-invariant direct methods | Absolute structure: Friedel pairs merged as equivalent data |
Secondary atom site location: difference Fourier map |
C24H26N2O7 | V = 1116.4 (3) Å3 |
Mr = 454.47 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 7.3998 (10) Å | µ = 0.10 mm−1 |
b = 16.383 (2) Å | T = 296 K |
c = 9.2162 (13) Å | 0.30 × 0.25 × 0.20 mm |
β = 92.322 (2)° |
Bruker SMART APEX II CCD diffractometer | 2612 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2352 reflections with I > 2σ(I) |
Tmin = 0.971, Tmax = 0.980 | Rint = 0.023 |
7148 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 1 restraint |
wR(F2) = 0.087 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.21 e Å−3 |
2612 reflections | Δρmin = −0.13 e Å−3 |
302 parameters | Absolute structure: Friedel pairs merged as equivalent data |
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 | 0.9756 (3) | 0.86809 (10) | 0.37052 (17) | 0.0497 (4) | |
O2 | 1.0016 (3) | 0.90832 (11) | 0.14679 (19) | 0.0571 (5) | |
O3 | 0.8961 (2) | 0.75590 (10) | 0.03780 (15) | 0.0361 (3) | |
O4 | 0.6197 (2) | 0.46524 (11) | 0.2027 (2) | 0.0518 (4) | |
O5 | 0.8933 (2) | 0.44686 (10) | 0.31575 (17) | 0.0438 (4) | |
O6 | 0.8228 (2) | 0.68765 (11) | 0.66980 (16) | 0.0445 (4) | |
O7 | 1.1799 (2) | 0.74245 (12) | 0.13801 (17) | 0.0483 (4) | |
N1 | 0.7652 (2) | 0.59843 (11) | 0.48365 (19) | 0.0342 (4) | |
N2 | 1.1043 (3) | 0.69448 (13) | −0.0887 (2) | 0.0429 (5) | |
H2 | 1.0138 | 0.6919 | −0.1538 | 0.043 (7)* | |
C1 | 0.9037 (3) | 0.81619 (15) | 0.4800 (2) | 0.0415 (5) | |
H1A | 0.8013 | 0.8434 | 0.5212 | 0.050* | |
H1B | 0.9953 | 0.8090 | 0.5573 | 0.050* | |
C2 | 0.9466 (3) | 0.85775 (14) | 0.2281 (2) | 0.0395 (5) | |
C3 | 0.8317 (3) | 0.78525 (13) | 0.1735 (2) | 0.0337 (4) | |
C4 | 0.8214 (3) | 0.71695 (12) | 0.2830 (2) | 0.0314 (4) | |
C5 | 0.7784 (3) | 0.63660 (14) | 0.2365 (2) | 0.0343 (4) | |
H5 | 0.7661 | 0.6238 | 0.1383 | 0.041* | |
C6 | 0.7561 (3) | 0.57932 (13) | 0.3391 (2) | 0.0331 (4) | |
C7 | 0.7254 (3) | 0.48743 (13) | 0.3259 (3) | 0.0382 (5) | |
C8 | 0.6437 (3) | 0.46579 (16) | 0.4706 (3) | 0.0479 (6) | |
H8A | 0.5127 | 0.4682 | 0.4625 | 0.057* | |
H8B | 0.6798 | 0.4113 | 0.5012 | 0.057* | |
C9 | 0.7175 (3) | 0.52940 (15) | 0.5779 (3) | 0.0442 (6) | |
H9A | 0.6265 | 0.5453 | 0.6454 | 0.053* | |
H9B | 0.8230 | 0.5090 | 0.6323 | 0.053* | |
C10 | 0.8130 (3) | 0.67425 (14) | 0.5379 (2) | 0.0342 (4) | |
C11 | 0.8446 (3) | 0.73440 (13) | 0.4266 (2) | 0.0326 (4) | |
C12 | 0.9214 (4) | 0.43939 (19) | 0.1647 (3) | 0.0581 (7) | |
H12A | 0.9934 | 0.3915 | 0.1447 | 0.070* | |
H12B | 0.9815 | 0.4873 | 0.1281 | 0.070* | |
C13 | 0.7343 (5) | 0.4315 (2) | 0.0987 (3) | 0.0685 (9) | |
H13A | 0.7230 | 0.4613 | 0.0078 | 0.082* | |
H13B | 0.7046 | 0.3746 | 0.0804 | 0.082* | |
C14 | 0.6397 (3) | 0.81741 (16) | 0.1294 (2) | 0.0432 (5) | |
H14A | 0.6488 | 0.8518 | 0.0444 | 0.052* | |
H14B | 0.5640 | 0.7712 | 0.1018 | 0.052* | |
C15 | 0.5467 (3) | 0.86541 (17) | 0.2454 (3) | 0.0510 (6) | |
H15A | 0.6108 | 0.9155 | 0.2638 | 0.076* | |
H15B | 0.5456 | 0.8338 | 0.3330 | 0.076* | |
H15C | 0.4247 | 0.8773 | 0.2127 | 0.076* | |
C16 | 1.0725 (3) | 0.73094 (14) | 0.0376 (2) | 0.0357 (5) | |
C17 | 1.2862 (3) | 0.66796 (18) | −0.1258 (3) | 0.0493 (6) | |
H17 | 1.3694 | 0.7138 | −0.1083 | 0.059* | |
C18 | 1.3521 (6) | 0.5967 (3) | −0.0323 (3) | 0.0880 (13) | |
H18A | 1.2645 | 0.5535 | −0.0383 | 0.132* | |
H18B | 1.3680 | 0.6143 | 0.0668 | 0.132* | |
H18C | 1.4653 | 0.5774 | −0.0662 | 0.132* | |
C19 | 1.2817 (3) | 0.64878 (15) | −0.2861 (2) | 0.0378 (5) | |
C20 | 1.2066 (3) | 0.57611 (15) | −0.3382 (2) | 0.0424 (5) | |
H20 | 1.1624 | 0.5383 | −0.2732 | 0.051* | |
C21 | 1.1968 (4) | 0.55937 (18) | −0.4847 (3) | 0.0517 (7) | |
H21 | 1.1485 | 0.5100 | −0.5175 | 0.062* | |
C22 | 1.2572 (4) | 0.6144 (2) | −0.5813 (3) | 0.0611 (8) | |
H22 | 1.2488 | 0.6030 | −0.6803 | 0.073* | |
C23 | 1.3300 (4) | 0.6861 (2) | −0.5336 (3) | 0.0696 (9) | |
H23 | 1.3713 | 0.7237 | −0.6003 | 0.084* | |
C24 | 1.3436 (4) | 0.70394 (18) | −0.3862 (3) | 0.0558 (7) | |
H24 | 1.3945 | 0.7531 | −0.3547 | 0.067* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0722 (12) | 0.0424 (9) | 0.0346 (8) | −0.0192 (9) | 0.0029 (8) | −0.0057 (7) |
O2 | 0.0855 (14) | 0.0408 (9) | 0.0462 (10) | −0.0161 (10) | 0.0177 (9) | −0.0003 (8) |
O3 | 0.0421 (8) | 0.0407 (8) | 0.0254 (7) | 0.0030 (7) | 0.0020 (6) | −0.0044 (6) |
O4 | 0.0513 (9) | 0.0465 (10) | 0.0567 (11) | −0.0033 (8) | −0.0082 (8) | −0.0087 (8) |
O5 | 0.0487 (9) | 0.0429 (9) | 0.0396 (8) | 0.0118 (7) | 0.0007 (7) | −0.0048 (7) |
O6 | 0.0530 (9) | 0.0532 (10) | 0.0274 (8) | 0.0067 (8) | −0.0001 (7) | −0.0026 (7) |
O7 | 0.0462 (9) | 0.0642 (12) | 0.0339 (8) | 0.0019 (8) | −0.0043 (7) | −0.0097 (8) |
N1 | 0.0365 (9) | 0.0356 (10) | 0.0306 (9) | 0.0042 (8) | 0.0044 (7) | 0.0025 (7) |
N2 | 0.0400 (10) | 0.0571 (13) | 0.0313 (9) | 0.0084 (9) | −0.0022 (8) | −0.0104 (9) |
C1 | 0.0527 (13) | 0.0394 (12) | 0.0324 (11) | −0.0061 (11) | 0.0010 (10) | −0.0039 (10) |
C2 | 0.0478 (12) | 0.0348 (12) | 0.0363 (12) | −0.0035 (10) | 0.0083 (10) | −0.0043 (10) |
C3 | 0.0405 (11) | 0.0331 (10) | 0.0274 (10) | 0.0012 (9) | 0.0020 (8) | −0.0041 (8) |
C4 | 0.0326 (10) | 0.0323 (10) | 0.0295 (10) | 0.0019 (8) | 0.0021 (8) | −0.0033 (8) |
C5 | 0.0413 (11) | 0.0341 (11) | 0.0274 (10) | −0.0003 (9) | −0.0010 (8) | −0.0046 (8) |
C6 | 0.0326 (10) | 0.0322 (11) | 0.0344 (11) | 0.0026 (8) | 0.0008 (8) | −0.0044 (9) |
C7 | 0.0394 (11) | 0.0310 (11) | 0.0441 (13) | 0.0014 (9) | 0.0010 (9) | 0.0002 (9) |
C8 | 0.0508 (13) | 0.0394 (13) | 0.0545 (15) | 0.0010 (11) | 0.0133 (11) | 0.0048 (11) |
C9 | 0.0528 (14) | 0.0399 (12) | 0.0408 (13) | 0.0058 (11) | 0.0130 (10) | 0.0095 (10) |
C10 | 0.0339 (10) | 0.0393 (11) | 0.0295 (10) | 0.0065 (9) | 0.0019 (8) | −0.0020 (9) |
C11 | 0.0343 (10) | 0.0357 (11) | 0.0278 (10) | 0.0018 (9) | 0.0016 (8) | −0.0045 (8) |
C12 | 0.0686 (18) | 0.0605 (17) | 0.0456 (14) | 0.0120 (14) | 0.0076 (13) | −0.0118 (13) |
C13 | 0.087 (2) | 0.0624 (19) | 0.0550 (16) | 0.0104 (16) | −0.0080 (15) | −0.0230 (15) |
C14 | 0.0458 (12) | 0.0446 (13) | 0.0390 (12) | 0.0085 (10) | 0.0000 (10) | −0.0004 (10) |
C15 | 0.0477 (13) | 0.0490 (14) | 0.0567 (15) | 0.0068 (12) | 0.0083 (11) | −0.0009 (12) |
C16 | 0.0439 (11) | 0.0357 (11) | 0.0276 (10) | 0.0011 (9) | 0.0021 (9) | −0.0009 (9) |
C17 | 0.0441 (13) | 0.0624 (17) | 0.0411 (13) | 0.0119 (11) | −0.0027 (10) | −0.0115 (12) |
C18 | 0.110 (3) | 0.115 (3) | 0.0382 (15) | 0.065 (3) | −0.0092 (16) | −0.0031 (17) |
C19 | 0.0324 (10) | 0.0446 (13) | 0.0365 (12) | 0.0058 (9) | 0.0046 (8) | −0.0024 (10) |
C20 | 0.0445 (12) | 0.0438 (13) | 0.0390 (12) | 0.0037 (10) | 0.0025 (10) | 0.0011 (10) |
C21 | 0.0482 (14) | 0.0552 (15) | 0.0512 (15) | 0.0099 (12) | −0.0054 (11) | −0.0172 (12) |
C22 | 0.0525 (15) | 0.092 (2) | 0.0383 (14) | 0.0138 (15) | 0.0034 (12) | −0.0036 (14) |
C23 | 0.0656 (18) | 0.093 (3) | 0.0515 (17) | −0.0036 (18) | 0.0146 (14) | 0.0258 (17) |
C24 | 0.0545 (15) | 0.0497 (15) | 0.0633 (18) | −0.0088 (12) | 0.0033 (13) | 0.0010 (13) |
O1—C2 | 1.333 (3) | C9—H9A | 0.970 |
O1—C1 | 1.438 (3) | C9—H9B | 0.970 |
O2—C2 | 1.199 (3) | C10—C11 | 1.448 (3) |
O3—C16 | 1.369 (3) | C12—C13 | 1.495 (5) |
O3—C3 | 1.439 (2) | C12—H12A | 0.970 |
O4—C7 | 1.400 (3) | C12—H12B | 0.970 |
O4—C13 | 1.419 (4) | C13—H13A | 0.970 |
O5—C7 | 1.416 (3) | C13—H13B | 0.970 |
O5—C12 | 1.421 (3) | C14—C15 | 1.515 (3) |
O6—C10 | 1.235 (3) | C14—H14A | 0.970 |
O7—C16 | 1.210 (3) | C14—H14B | 0.970 |
N1—C6 | 1.368 (3) | C15—H15A | 0.960 |
N1—C10 | 1.380 (3) | C15—H15B | 0.960 |
N1—C9 | 1.478 (3) | C15—H15C | 0.960 |
N2—C16 | 1.337 (3) | C17—C19 | 1.510 (3) |
N2—C17 | 1.468 (3) | C17—C18 | 1.519 (4) |
N2—H2 | 0.88 | C17—H17 | 0.980 |
C1—C11 | 1.487 (3) | C18—H18A | 0.960 |
C1—H1A | 0.970 | C18—H18B | 0.960 |
C1—H1B | 0.970 | C18—H18C | 0.960 |
C2—C3 | 1.534 (3) | C19—C24 | 1.382 (4) |
C3—C4 | 1.511 (3) | C19—C20 | 1.391 (3) |
C3—C14 | 1.553 (3) | C20—C21 | 1.377 (3) |
C4—C11 | 1.358 (3) | C20—H20 | 0.930 |
C4—C5 | 1.417 (3) | C21—C22 | 1.356 (4) |
C5—C6 | 1.347 (3) | C21—H21 | 0.930 |
C5—H5 | 0.930 | C22—C23 | 1.359 (5) |
C6—C7 | 1.527 (3) | C22—H22 | 0.930 |
C7—C8 | 1.528 (3) | C23—C24 | 1.390 (4) |
C8—C9 | 1.523 (4) | C23—H23 | 0.930 |
C8—H8A | 0.970 | C24—H24 | 0.930 |
C8—H8B | 0.970 | ||
C2—O1—C1 | 124.53 (18) | O5—C12—C13 | 103.7 (2) |
C16—O3—C3 | 116.79 (16) | O5—C12—H12A | 111.0 |
C7—O4—C13 | 108.6 (2) | C13—C12—H12A | 111.0 |
C7—O5—C12 | 105.57 (19) | O5—C12—H12B | 111.0 |
C6—N1—C10 | 124.12 (18) | C13—C12—H12B | 111.0 |
C6—N1—C9 | 113.22 (18) | H12A—C12—H12B | 109.0 |
C10—N1—C9 | 122.67 (18) | O4—C13—C12 | 105.1 (2) |
C16—N2—C17 | 122.03 (19) | O4—C13—H13A | 110.7 |
C16—N2—H2 | 117.3 | C12—C13—H13A | 110.7 |
C17—N2—H2 | 120.3 | O4—C13—H13B | 110.7 |
O1—C1—C11 | 114.38 (17) | C12—C13—H13B | 110.7 |
O1—C1—H1A | 108.7 | H13A—C13—H13B | 108.8 |
C11—C1—H1A | 108.7 | C15—C14—C3 | 115.36 (19) |
O1—C1—H1B | 108.7 | C15—C14—H14A | 108.4 |
C11—C1—H1B | 108.7 | C3—C14—H14A | 108.4 |
H1A—C1—H1B | 107.6 | C15—C14—H14B | 108.4 |
O2—C2—O1 | 118.8 (2) | C3—C14—H14B | 108.4 |
O2—C2—C3 | 121.9 (2) | H14A—C14—H14B | 107.5 |
O1—C2—C3 | 119.10 (18) | C14—C15—H15A | 109.5 |
O3—C3—C4 | 111.14 (17) | C14—C15—H15B | 109.5 |
O3—C3—C2 | 110.17 (16) | H15A—C15—H15B | 109.5 |
C4—C3—C2 | 113.39 (17) | C14—C15—H15C | 109.5 |
O3—C3—C14 | 102.54 (16) | H15A—C15—H15C | 109.5 |
C4—C3—C14 | 110.84 (18) | H15B—C15—H15C | 109.5 |
C2—C3—C14 | 108.18 (18) | O7—C16—N2 | 127.0 (2) |
C11—C4—C5 | 120.59 (19) | O7—C16—O3 | 123.32 (19) |
C11—C4—C3 | 119.16 (18) | N2—C16—O3 | 109.65 (18) |
C5—C4—C3 | 120.17 (18) | N2—C17—C19 | 107.78 (18) |
C6—C5—C4 | 117.85 (19) | N2—C17—C18 | 111.8 (3) |
C6—C5—H5 | 121.1 | C19—C17—C18 | 112.9 (2) |
C4—C5—H5 | 121.1 | N2—C17—H17 | 108.1 |
C5—C6—N1 | 121.5 (2) | C19—C17—H17 | 108.1 |
C5—C6—C7 | 130.8 (2) | C18—C17—H17 | 108.1 |
N1—C6—C7 | 107.74 (18) | C17—C18—H18A | 109.5 |
O4—C7—O5 | 106.74 (19) | C17—C18—H18B | 109.5 |
O4—C7—C6 | 113.41 (19) | H18A—C18—H18B | 109.5 |
O5—C7—C6 | 109.87 (18) | C17—C18—H18C | 109.5 |
O4—C7—C8 | 114.8 (2) | H18A—C18—H18C | 109.5 |
O5—C7—C8 | 109.14 (19) | H18B—C18—H18C | 109.5 |
C6—C7—C8 | 102.82 (19) | C24—C19—C20 | 117.9 (2) |
C9—C8—C7 | 105.3 (2) | C24—C19—C17 | 121.5 (2) |
C9—C8—H8A | 110.7 | C20—C19—C17 | 120.6 (2) |
C7—C8—H8A | 110.7 | C21—C20—C19 | 120.9 (2) |
C9—C8—H8B | 110.7 | C21—C20—H20 | 119.6 |
C7—C8—H8B | 110.7 | C19—C20—H20 | 119.6 |
H8A—C8—H8B | 108.8 | C22—C21—C20 | 120.4 (3) |
N1—C9—C8 | 103.28 (19) | C22—C21—H21 | 119.8 |
N1—C9—H9A | 111.1 | C20—C21—H21 | 119.8 |
C8—C9—H9A | 111.1 | C21—C22—C23 | 119.9 (3) |
N1—C9—H9B | 111.1 | C21—C22—H22 | 120.0 |
C8—C9—H9B | 111.1 | C23—C22—H22 | 120.0 |
H9A—C9—H9B | 109.1 | C22—C23—C24 | 120.7 (3) |
O6—C10—N1 | 121.4 (2) | C22—C23—H23 | 119.6 |
O6—C10—C11 | 124.9 (2) | C24—C23—H23 | 119.6 |
N1—C10—C11 | 113.73 (18) | C19—C24—C23 | 120.1 (3) |
C4—C11—C10 | 121.9 (2) | C19—C24—H24 | 119.9 |
C4—C11—C1 | 122.42 (19) | C23—C24—H24 | 119.9 |
C10—C11—C1 | 115.64 (17) | ||
C2—O1—C1—C11 | 19.3 (3) | C6—N1—C9—C8 | −9.5 (2) |
C1—O1—C2—O2 | 174.3 (2) | C10—N1—C9—C8 | 170.22 (18) |
C1—O1—C2—C3 | −1.0 (3) | C7—C8—C9—N1 | 23.0 (2) |
C16—O3—C3—C4 | −68.2 (2) | C6—N1—C10—O6 | −178.39 (19) |
C16—O3—C3—C2 | 58.3 (2) | C9—N1—C10—O6 | 1.9 (3) |
C16—O3—C3—C14 | 173.30 (18) | C6—N1—C10—C11 | 3.0 (3) |
O2—C2—C3—O3 | 38.1 (3) | C9—N1—C10—C11 | −176.68 (18) |
O1—C2—C3—O3 | −146.7 (2) | C5—C4—C11—C10 | −5.0 (3) |
O2—C2—C3—C4 | 163.4 (2) | C3—C4—C11—C10 | 171.69 (18) |
O1—C2—C3—C4 | −21.4 (3) | C5—C4—C11—C1 | 175.1 (2) |
O2—C2—C3—C14 | −73.2 (3) | C3—C4—C11—C1 | −8.2 (3) |
O1—C2—C3—C14 | 102.0 (2) | O6—C10—C11—C4 | −176.1 (2) |
O3—C3—C4—C11 | 150.41 (18) | N1—C10—C11—C4 | 2.5 (3) |
C2—C3—C4—C11 | 25.7 (3) | O6—C10—C11—C1 | 3.8 (3) |
C14—C3—C4—C11 | −96.2 (2) | N1—C10—C11—C1 | −177.63 (18) |
O3—C3—C4—C5 | −32.9 (3) | O1—C1—C11—C4 | −14.4 (3) |
C2—C3—C4—C5 | −157.67 (18) | O1—C1—C11—C10 | 165.72 (18) |
C14—C3—C4—C5 | 80.4 (2) | C7—O5—C12—C13 | −31.7 (3) |
C11—C4—C5—C6 | 2.0 (3) | C7—O4—C13—C12 | −3.3 (3) |
C3—C4—C5—C6 | −174.58 (19) | O5—C12—C13—O4 | 21.5 (3) |
C4—C5—C6—N1 | 3.3 (3) | O3—C3—C14—C15 | −170.4 (2) |
C4—C5—C6—C7 | −174.3 (2) | C4—C3—C14—C15 | 70.9 (3) |
C10—N1—C6—C5 | −6.0 (3) | C2—C3—C14—C15 | −54.0 (3) |
C9—N1—C6—C5 | 173.7 (2) | C17—N2—C16—O7 | −4.6 (4) |
C10—N1—C6—C7 | 172.05 (18) | C17—N2—C16—O3 | 174.3 (2) |
C9—N1—C6—C7 | −8.3 (2) | C3—O3—C16—O7 | −10.1 (3) |
C13—O4—C7—O5 | −16.4 (3) | C3—O3—C16—N2 | 170.89 (18) |
C13—O4—C7—C6 | 104.7 (2) | C16—N2—C17—C19 | −166.5 (2) |
C13—O4—C7—C8 | −137.5 (2) | C16—N2—C17—C18 | 68.9 (3) |
C12—O5—C7—O4 | 30.5 (3) | N2—C17—C19—C24 | 99.6 (3) |
C12—O5—C7—C6 | −92.8 (2) | C18—C17—C19—C24 | −136.5 (3) |
C12—O5—C7—C8 | 155.1 (2) | N2—C17—C19—C20 | −77.4 (3) |
C5—C6—C7—O4 | −35.3 (3) | C18—C17—C19—C20 | 46.5 (3) |
N1—C6—C7—O4 | 146.85 (19) | C24—C19—C20—C21 | 0.9 (4) |
C5—C6—C7—O5 | 84.0 (3) | C17—C19—C20—C21 | 177.9 (2) |
N1—C6—C7—O5 | −93.8 (2) | C19—C20—C21—C22 | −1.3 (4) |
C5—C6—C7—C8 | −159.9 (2) | C20—C21—C22—C23 | 0.8 (4) |
N1—C6—C7—C8 | 22.3 (2) | C21—C22—C23—C24 | 0.0 (5) |
O4—C7—C8—C9 | −151.2 (2) | C20—C19—C24—C23 | 0.0 (4) |
O5—C7—C8—C9 | 89.0 (2) | C17—C19—C24—C23 | −177.1 (3) |
C6—C7—C8—C9 | −27.6 (2) | C22—C23—C24—C19 | −0.4 (5) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O6i | 0.88 | 2.11 | 2.988 (2) | 173 |
Symmetry code: (i) x, y, z−1. |
Experimental details
Crystal data | |
Chemical formula | C24H26N2O7 |
Mr | 454.47 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 296 |
a, b, c (Å) | 7.3998 (10), 16.383 (2), 9.2162 (13) |
β (°) | 92.322 (2) |
V (Å3) | 1116.4 (3) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.30 × 0.25 × 0.20 |
Data collection | |
Diffractometer | Bruker SMART APEX II CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.971, 0.980 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7148, 2612, 2352 |
Rint | 0.023 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.087, 1.06 |
No. of reflections | 2612 |
No. of parameters | 302 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.21, −0.13 |
Absolute structure | Friedel pairs merged as equivalent data |
Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O6i | 0.88 | 2.11 | 2.988 (2) | 172.5 |
Symmetry code: (i) x, y, z−1. |
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The method for resolution of a tertiary alcohol using a chiral isocyanate reagent has been widely applied (Gibbs et al., 1989). The title compound is a key intermediate in the resolution process of alcohol 1 using the (S)-isocyanate 2 (Scheme 2).
On the basis of the unchanging S configuration of C17, the molecular structure (Figure 1) indicates that the chiral C atom C3 adopts an S configuration. The six-membered lactone ring is twisted with an O1/C2/C3/C4 torsion angle of -21.4 (3) °. The pyrrole ring is also twisted, with a N1/C6/C7/C8 torsion angle of 22.3 (2) °. N—H···O hydrogen bonds exist between molecules, linking them into chains along the c axis.