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| CRYSTALLOGRAPHIC COMMUNICATIONS |
accesstert-Butyl 3-oxo-2-oxa-5-azabicyclo[2.2.1]heptane-5-carboxylate
aCNRS, Institut de Biologie Moléculaire et Cellulaire, Laboratoire d'Immunologie et Chimie Thérapeutiques, 15 rue René Descartes, F-67000 Strasbourg, France, and bLaboratoire de Cristallographie et Modélisation des Matériaux Minéraux et Biologiques (LCM3B), UMR No. 7036, Nancy Université, Faculté des Sciences et Techniques, BP 239, 54506 Vandoeuvre lès Nancy Cedex, France
*Correspondence e-mail: claude.didierjean@lcm3b.uhp-nancy.fr
The title compound, C10H15NO4, also known as N-tert-butyloxycarbonyl-allohydroxy-L-proline lactone, is quite similar to N-acetyl-allohydroxy-L-proline lactone [Lenstra, Petit & Geise (1979![[Lenstra, A. T. H., Petit, G. H. & Geise, H. J. (1979). Cryst. Struct. Commun. 8, 1023-1029.]](../../../../../../logos/arrows/e_arr.gif "Lenstra, A. T. H., Petit, G. H. & Geise, H. J. (1979). Cryst. Struct. Commun. 8, 1023-1029.")
). Cryst. Struct. Commun. 8, 1023–1029], whereby both carbonyl groups point roughly in the same direction because of the trans conformation of the peptide bond.
Related literature
For general background, see: Allen (2002). For related structures, see: Didier et al. (2004); Lenstra et al. (1979); Papaioannou et al. (1989). For related synthesis, see: Gómez-Vidal & Silverman (2001). For related literature, see: Flack & Schwarzenbach (1988).
![[Scheme 1]](ww2125scheme1.gif)
Experimental
Crystal data
|
Data collection: COLLECT (Nonius, 1998); cell SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
Supporting information
contains datablocks global, I. DOI: 10.1107/S1600536808030651/ww2125sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536808030651/ww2125Isup2.hkl
The title compound was prepared in 80% from N-Boc-trans-4-hydroxyproline following the a described procedure (Gómez-Vidal & Silverman, 2001) and was crystallized by slow evaporation of a cyclohexane/ethyl acetate (3:2, v/v) solution.
Because of the lack of any significant effects, the absolute configurations of the title compound could not be determined from the diffraction experiments but was known from the method of synthesis. The origin was fixed by floating-origin restraints (Flack & Schwarzenbach, 1988). All H atoms were located in difference Fourier maps. The C-bonded H atoms were placed at calculated positions and refined using a riding model, with C—H distances of 0.93–0.96 Å. The H-atom Uiso parameters were fixed at 1.2Ueq(C) for methine and methylene C—H and at 1.5Ueq(C) for methyl C—H.
Data collection: COLLECT (Bruker, 2004); cell SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).
![[Figure 1]](./ww2125fig1thm.gif) | Fig. 1. The molecular structure of title compound showing the atom-numbering scheme. All non-H atoms are represented by 50% probability displacement ellipsoids. |
| C10H15NO4 | F(000) = 228 |
| Mr = 213.23 | Dx = 1.359 Mg m−3 |
| Monoclinic, P21 | Mo Kα radiation, λ = 0.7107 Å |
| Hall symbol: P 2yb | Cell parameters from 11845 reflections |
| a = 6.0710 (7) Å | θ = 0.4–26.4° |
| b = 9.3703 (11) Å | µ = 0.11 mm−1 |
| c = 9.3002 (10) Å | T = 100 K |
| β = 100.013 (5)° | Prism, colourless |
| V = 521.00 (10) Å3 | 0.3 × 0.2 × 0.2 mm |
| Z = 2 |
| Nonius KappaCCD area-detector diffractometer | 1054 reflections with I > 2σ(I) |
| Radiation source: fine-focus sealed tube | Rint = 0.066 |
| Graphite monochromator | θmax = 26.6°, θmin = 3.1° |
| ω and ϕ scans | h = −7→7 |
| 5951 measured reflections | k = −11→11 |
| 1143 independent reflections | l = −11→11 |
| Refinement on F2 | 1 restraint |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.052 | w = 1/[σ2(Fo2) + (0.0035P)2 + 0.6362P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.102 | (Δ/σ)max < 0.001 |
| S = 1.20 | Δρmax = 0.23 e Å−3 |
| 1143 reflections | Δρmin = −0.22 e Å−3 |
| 139 parameters |
| C10H15NO4 | V = 521.00 (10) Å3 |
| Mr = 213.23 | Z = 2 |
| Monoclinic, P21 | Mo Kα radiation |
| a = 6.0710 (7) Å | µ = 0.11 mm−1 |
| b = 9.3703 (11) Å | T = 100 K |
| c = 9.3002 (10) Å | 0.3 × 0.2 × 0.2 mm |
| β = 100.013 (5)° |
| Nonius KappaCCD area-detector diffractometer | 1054 reflections with I > 2σ(I) |
| 5951 measured reflections | Rint = 0.066 |
| 1143 independent reflections |
| R[F2 > 2σ(F2)] = 0.052 | 1 restraint |
| wR(F2) = 0.102 | H-atom parameters constrained |
| S = 1.20 | Δρmax = 0.23 e Å−3 |
| 1143 reflections | Δρmin = −0.22 e Å−3 |
| 139 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. |
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.3991 (4) | 0.3322 (3) | 0.3133 (3) | 0.0243 (6) | |
| O2 | 0.0303 (4) | 0.2997 (3) | 0.2103 (3) | 0.0280 (7) | |
| O3 | 0.3864 (4) | −0.0967 (3) | 0.1079 (3) | 0.0262 (7) | |
| O4 | 0.0299 (5) | −0.1077 (3) | 0.1467 (3) | 0.0319 (7) | |
| N1 | 0.3137 (5) | 0.1896 (4) | 0.1226 (4) | 0.0230 (7) | |
| C1 | 0.3539 (7) | 0.4316 (4) | 0.4288 (4) | 0.0249 (9) | |
| C2 | 0.2354 (7) | 0.5650 (4) | 0.3607 (5) | 0.0306 (10) | |
| H2A | 0.3194 | 0.6052 | 0.2893 | 0.046* | |
| H2B | 0.2265 | 0.6356 | 0.4372 | 0.046* | |
| H2C | 0.0842 | 0.54 | 0.3117 | 0.046* | |
| C3 | 0.2204 (8) | 0.3563 (5) | 0.5297 (5) | 0.0315 (10) | |
| H3A | 0.075 | 0.3274 | 0.4744 | 0.047* | |
| H3B | 0.1977 | 0.4212 | 0.6085 | 0.047* | |
| H3C | 0.3024 | 0.2717 | 0.5715 | 0.047* | |
| C4 | 0.5884 (6) | 0.4670 (4) | 0.5062 (5) | 0.0266 (9) | |
| H4A | 0.6574 | 0.3816 | 0.5556 | 0.04* | |
| H4B | 0.5813 | 0.5423 | 0.5784 | 0.04* | |
| H4C | 0.678 | 0.5001 | 0.4347 | 0.04* | |
| C5 | 0.2283 (6) | 0.2759 (4) | 0.2159 (4) | 0.0227 (8) | |
| C6 | 0.5472 (7) | 0.1381 (4) | 0.1373 (5) | 0.0250 (9) | |
| H6A | 0.6091 | 0.1101 | 0.239 | 0.03* | |
| H6B | 0.646 | 0.21 | 0.1032 | 0.03* | |
| C7 | 0.5098 (7) | 0.0093 (4) | 0.0356 (4) | 0.0265 (9) | |
| H7 | 0.648 | −0.0281 | 0.004 | 0.032* | |
| C8 | 0.3299 (7) | 0.0625 (5) | −0.0887 (4) | 0.0259 (9) | |
| H8A | 0.3762 | 0.1478 | −0.1388 | 0.031* | |
| H8B | 0.273 | −0.0127 | −0.1603 | 0.031* | |
| C9 | 0.1701 (6) | 0.0969 (4) | 0.0167 (4) | 0.0233 (9) | |
| H9 | 0.0204 | 0.1361 | −0.0275 | 0.028* | |
| C10 | 0.1710 (7) | −0.0459 (4) | 0.0960 (4) | 0.0256 (9) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0249 (14) | 0.0180 (14) | 0.0299 (14) | −0.0012 (12) | 0.0044 (12) | −0.0053 (12) |
| O2 | 0.0234 (14) | 0.0253 (16) | 0.0352 (16) | 0.0018 (13) | 0.0050 (12) | −0.0054 (13) |
| O3 | 0.0253 (15) | 0.0189 (14) | 0.0349 (16) | −0.0018 (13) | 0.0067 (12) | 0.0007 (13) |
| O4 | 0.0344 (17) | 0.0263 (16) | 0.0359 (16) | −0.0089 (14) | 0.0091 (13) | 0.0022 (14) |
| N1 | 0.0215 (17) | 0.0192 (17) | 0.0275 (18) | 0.0024 (14) | 0.0017 (14) | −0.0023 (15) |
| C1 | 0.027 (2) | 0.018 (2) | 0.031 (2) | 0.0018 (17) | 0.0092 (17) | −0.0050 (17) |
| C2 | 0.034 (2) | 0.018 (2) | 0.039 (2) | 0.0029 (18) | 0.0049 (19) | −0.0017 (19) |
| C3 | 0.037 (2) | 0.023 (2) | 0.035 (2) | −0.0045 (18) | 0.0101 (19) | −0.0047 (19) |
| C4 | 0.026 (2) | 0.020 (2) | 0.034 (2) | −0.0009 (17) | 0.0064 (17) | −0.0039 (18) |
| C5 | 0.023 (2) | 0.0157 (19) | 0.029 (2) | −0.0012 (16) | 0.0028 (16) | 0.0015 (16) |
| C6 | 0.024 (2) | 0.021 (2) | 0.030 (2) | −0.0009 (17) | 0.0057 (16) | −0.0024 (17) |
| C7 | 0.028 (2) | 0.022 (2) | 0.030 (2) | −0.0006 (18) | 0.0099 (19) | −0.0045 (18) |
| C8 | 0.031 (2) | 0.019 (2) | 0.028 (2) | −0.0005 (17) | 0.0056 (17) | −0.0007 (18) |
| C9 | 0.0238 (19) | 0.0187 (19) | 0.027 (2) | −0.0022 (17) | 0.0049 (17) | −0.0039 (16) |
| C10 | 0.031 (2) | 0.020 (2) | 0.025 (2) | −0.0038 (18) | 0.0024 (17) | −0.0047 (17) |
| O1—C5 | 1.359 (5) | C3—H3B | 0.98 |
| O1—C1 | 1.484 (5) | C3—H3C | 0.98 |
| O2—C5 | 1.215 (5) | C4—H4A | 0.98 |
| O3—C10 | 1.377 (5) | C4—H4B | 0.98 |
| O3—C7 | 1.475 (5) | C4—H4C | 0.98 |
| O4—C10 | 1.196 (5) | C6—C7 | 1.526 (6) |
| N1—C5 | 1.353 (5) | C6—H6A | 0.99 |
| N1—C9 | 1.478 (5) | C6—H6B | 0.99 |
| N1—C6 | 1.481 (5) | C7—C8 | 1.529 (6) |
| C1—C4 | 1.516 (5) | C7—H7 | 1 |
| C1—C3 | 1.516 (6) | C8—C9 | 1.528 (6) |
| C1—C2 | 1.524 (6) | C8—H8A | 0.99 |
| C2—H2A | 0.98 | C8—H8B | 0.99 |
| C2—H2B | 0.98 | C9—C10 | 1.528 (6) |
| C2—H2C | 0.98 | C9—H9 | 1 |
| C3—H3A | 0.98 | ||
| C5—O1—C1 | 120.7 (3) | O2—C5—O1 | 126.3 (4) |
| C10—O3—C7 | 106.3 (3) | N1—C5—O1 | 109.0 (3) |
| C5—N1—C9 | 122.1 (3) | N1—C6—C7 | 99.4 (3) |
| C5—N1—C6 | 127.1 (3) | N1—C6—H6A | 111.9 |
| C9—N1—C6 | 108.3 (3) | C7—C6—H6A | 111.9 |
| O1—C1—C4 | 101.8 (3) | N1—C6—H6B | 111.9 |
| O1—C1—C3 | 110.0 (3) | C7—C6—H6B | 111.9 |
| C4—C1—C3 | 111.5 (4) | H6A—C6—H6B | 109.6 |
| O1—C1—C2 | 110.3 (3) | O3—C7—C6 | 106.4 (3) |
| C4—C1—C2 | 110.7 (3) | O3—C7—C8 | 102.2 (3) |
| C3—C1—C2 | 112.0 (3) | C6—C7—C8 | 102.7 (3) |
| C1—C2—H2A | 109.5 | O3—C7—H7 | 114.7 |
| C1—C2—H2B | 109.5 | C6—C7—H7 | 114.7 |
| H2A—C2—H2B | 109.5 | C8—C7—H7 | 114.7 |
| C1—C2—H2C | 109.5 | C9—C8—C7 | 91.9 (3) |
| H2A—C2—H2C | 109.5 | C9—C8—H8A | 113.3 |
| H2B—C2—H2C | 109.5 | C7—C8—H8A | 113.3 |
| C1—C3—H3A | 109.5 | C9—C8—H8B | 113.3 |
| C1—C3—H3B | 109.5 | C7—C8—H8B | 113.3 |
| H3A—C3—H3B | 109.5 | H8A—C8—H8B | 110.6 |
| C1—C3—H3C | 109.5 | N1—C9—C10 | 103.9 (3) |
| H3A—C3—H3C | 109.5 | N1—C9—C8 | 100.6 (3) |
| H3B—C3—H3C | 109.5 | C10—C9—C8 | 100.1 (3) |
| C1—C4—H4A | 109.5 | N1—C9—H9 | 116.5 |
| C1—C4—H4B | 109.5 | C10—C9—H9 | 116.5 |
| H4A—C4—H4B | 109.5 | C8—C9—H9 | 116.5 |
| C1—C4—H4C | 109.5 | O4—C10—O3 | 122.4 (4) |
| H4A—C4—H4C | 109.5 | O4—C10—C9 | 132.2 (4) |
| H4B—C4—H4C | 109.5 | O3—C10—C9 | 105.4 (3) |
| O2—C5—N1 | 124.7 (4) | ||
| C5—O1—C1—C4 | −178.9 (3) | O3—C7—C8—C9 | 53.1 (3) |
| C5—O1—C1—C3 | 62.7 (5) | C6—C7—C8—C9 | −57.1 (3) |
| C5—O1—C1—C2 | −61.3 (4) | C5—N1—C9—C10 | −93.9 (4) |
| C9—N1—C5—O2 | −9.6 (6) | C6—N1—C9—C10 | 69.1 (4) |
| C6—N1—C5—O2 | −169.3 (4) | C5—N1—C9—C8 | 162.7 (3) |
| C9—N1—C5—O1 | 171.3 (3) | C6—N1—C9—C8 | −34.2 (4) |
| C6—N1—C5—O1 | 11.6 (5) | C7—C8—C9—N1 | 53.9 (3) |
| C1—O1—C5—O2 | 0.9 (6) | C7—C8—C9—C10 | −52.5 (3) |
| C1—O1—C5—N1 | 179.9 (3) | C7—O3—C10—O4 | −178.8 (4) |
| C5—N1—C6—C7 | 159.9 (4) | C7—O3—C10—C9 | −1.3 (4) |
| C9—N1—C6—C7 | −2.1 (4) | N1—C9—C10—O4 | 109.5 (5) |
| C10—O3—C7—C6 | 73.2 (4) | C8—C9—C10—O4 | −146.8 (4) |
| C10—O3—C7—C8 | −34.2 (4) | N1—C9—C10—O3 | −67.7 (3) |
| N1—C6—C7—O3 | −69.0 (4) | C8—C9—C10—O3 | 36.1 (4) |
| N1—C6—C7—C8 | 38.0 (4) |
Experimental details
| Crystal data | |
| Chemical formula | C10H15NO4 |
| Mr | 213.23 |
| Crystal system, space group | Monoclinic, P21 |
| Temperature (K) | 100 |
| a, b, c (Å) | 6.0710 (7), 9.3703 (11), 9.3002 (10) |
| β (°) | 100.013 (5) |
| V (Å3) | 521.00 (10) |
| Z | 2 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.11 |
| Crystal size (mm) | 0.3 × 0.2 × 0.2 |
| Data collection | |
| Diffractometer | Nonius KappaCCD area-detector diffractometer |
| Absorption correction | – |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 5951, 1143, 1054 |
| Rint | 0.066 |
| (sin θ/λ)max (Å−1) | 0.629 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.102, 1.20 |
| No. of reflections | 1143 |
| No. of parameters | 139 |
| No. of restraints | 1 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.23, −0.22 |
Computer programs: COLLECT (Bruker, 2004), SCALEPACK (Otwinowski & Minor, 1997), DENZO (Otwinowski & Minor, 1997) and SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
Footnotes
‡Additional correspondence author, email: g.guichard@ibmc.u-strasbg.fr
Acknowledgements
The authors thank the Service Commun de Diffraction X (Nancy Université) for providing access to crystallographic experimental facilities.
References
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
N-tert-Butyloxycarbonyl-allohydroxy-L-proline lactone is prepared in one step under Mitsunobu conditions starting from corresponding trans-4-hydroxyproline. As previously described (Gómez-Vidal & Silverman, 2001), this lactone is a useful derivative that can be readily transformed to N-Boc-cis-4-hydroxyl-L-prolinemethyl ester by quantitative trans-esterification with methanol in the presence of sodium azide. Further transformation of the hydroxyl group to an azido group in the presence of diphenylphosphorylazide (DPPA) under Mistunobu conditions affords N-Boc-trans-4-azido-L-proline methyl ester, a useful building block for the preparation of 4-aminoproline containing molecules.
A search of the Cambridge Structural Database (CSD, Version 5.29; Allen, 2002) for allohydroxy-L-proline lacton gave rise to 3 hits: (1S,4S)-N-acetyl-3-oxo-5-aza-2-oxabicyclo[2.2.1]heptane (Lenstra et al., 1979); N-triphenylmethyl-2-oxa-5-azabicyclo[2.2.1]heptan-3-one (Papaioannou et al., 1989); tert-butyl 7-chloro-6-methyl-2,3-dihydro-2-oxo-6H-3,10b-methano-1,4- dioxazino[3,2-c](2,1)benzoxazine-4(4aH)-carboxylate (Didier et al., 2004). In the four structures the pyrrolidine ring (N1/C6/C7/C8/C9 numbering in the title compound) adopts the same envelope conformation with C8 out of the mean plane defined by N1, C6, C7 and C9. Three structures consists of an amide bond: the title compound, the N-acetyl-allohydroxy-L-proline lacton and the tert-butyl- 7-chloro-6-methyl-2,3-dihydro-2-oxo-6H-3,10b-methano-1,4- dioxazino(3,2-c)(2,1)benzoxazine-4(4aH)-carboxylate. The two first structures exhibit a quite similar structure with a nearly planar trans- amide bond. In the last one, the peptide bond is cis- and the nitrogen atom of the pyrrolidine ring exhibits an observable pyramidalization. Indeed, the sum of bond angles around the nitrogen atom is of 347.9° whereas of 357.9° and 357.4° in the two first structures.