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Acta Crystallogr Sect E Struct Rep Online. 2008 October 1; 64(Pt 10): o2039.
Published online 2008 September 30. doi:  10.1107/S1600536808030651
PMCID: PMC2959344

tert-Butyl 3-oxo-2-oxa-5-aza­bicyclo­[2.2.1]heptane-5-carboxyl­ate

Abstract

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 [triangle]). 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 [triangle]). For related structures, see: Didier et al. (2004 [triangle]); Lenstra et al. (1979 [triangle]); Papaioannou et al. (1989 [triangle]). For related synthesis, see: Gómez-Vidal & Silverman (2001 [triangle]). For related literature, see: Flack & Schwarzenbach (1988 [triangle]).

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Object name is e-64-o2039-scheme1.jpg

Experimental

Crystal data

  • C10H15NO4
  • M r = 213.23
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-64-o2039-efi1.jpg
  • a = 6.0710 (7) Å
  • b = 9.3703 (11) Å
  • c = 9.3002 (10) Å
  • β = 100.013 (5)°
  • V = 521.00 (10) Å3
  • Z = 2
  • Mo Kα radiation
  • μ = 0.10 mm−1
  • T = 100 (2) K
  • 0.3 × 0.2 × 0.2 mm

Data collection

  • Nonius KappaCCD area-detector diffractometer
  • Absorption correction: none
  • 5951 measured reflections
  • 1143 independent reflections
  • 1054 reflections with I > 2σ(I)
  • R int = 0.066

Refinement

  • R[F 2 > 2σ(F 2)] = 0.052
  • wR(F 2) = 0.102
  • S = 1.20
  • 1143 reflections
  • 139 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 0.23 e Å−3
  • Δρmin = −0.22 e Å−3

Data collection: COLLECT (Nonius, 1998 [triangle]); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 [triangle]); data reduction: DENZO (Otwinowski & Minor, 1997 [triangle]) and SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808030651/ww2125sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808030651/ww2125Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authors thank the Service Commun de Diffraction X (Nancy Université) for providing access to crystallographic experimental facilities.

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

Because of the lack of any significant anomalous dispersion 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.

Figures

Fig. 1.
The molecular structure of title compound showing the atom-numbering scheme. All non-H atoms are represented by 50% probability displacement ellipsoids.

Crystal data

C10H15NO4F(000) = 228
Mr = 213.23Dx = 1.359 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.7107 Å
Hall symbol: P 2ybCell parameters from 11845 reflections
a = 6.0710 (7) Åθ = 0.4–26.4°
b = 9.3703 (11) ŵ = 0.11 mm1
c = 9.3002 (10) ÅT = 100 K
β = 100.013 (5)°Prism, colourless
V = 521.00 (10) Å30.3 × 0.2 × 0.2 mm
Z = 2

Data collection

Nonius KappaCCD area-detector diffractometer1054 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.066
graphiteθmax = 26.6°, θmin = 3.1°
ω and [var phi] scansh = −7→7
5951 measured reflectionsk = −11→11
1143 independent reflectionsl = −11→11

Refinement

Refinement on F21 restraint
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.052w = 1/[σ2(Fo2) + (0.0035P)2 + 0.6362P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.102(Δ/σ)max < 0.001
S = 1.20Δρmax = 0.23 e Å3
1143 reflectionsΔρmin = −0.22 e Å3
139 parameters

Special details

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
O10.3991 (4)0.3322 (3)0.3133 (3)0.0243 (6)
O20.0303 (4)0.2997 (3)0.2103 (3)0.0280 (7)
O30.3864 (4)−0.0967 (3)0.1079 (3)0.0262 (7)
O40.0299 (5)−0.1077 (3)0.1467 (3)0.0319 (7)
N10.3137 (5)0.1896 (4)0.1226 (4)0.0230 (7)
C10.3539 (7)0.4316 (4)0.4288 (4)0.0249 (9)
C20.2354 (7)0.5650 (4)0.3607 (5)0.0306 (10)
H2A0.31940.60520.28930.046*
H2B0.22650.63560.43720.046*
H2C0.08420.540.31170.046*
C30.2204 (8)0.3563 (5)0.5297 (5)0.0315 (10)
H3A0.0750.32740.47440.047*
H3B0.19770.42120.60850.047*
H3C0.30240.27170.57150.047*
C40.5884 (6)0.4670 (4)0.5062 (5)0.0266 (9)
H4A0.65740.38160.55560.04*
H4B0.58130.54230.57840.04*
H4C0.6780.50010.43470.04*
C50.2283 (6)0.2759 (4)0.2159 (4)0.0227 (8)
C60.5472 (7)0.1381 (4)0.1373 (5)0.0250 (9)
H6A0.60910.11010.2390.03*
H6B0.6460.210.10320.03*
C70.5098 (7)0.0093 (4)0.0356 (4)0.0265 (9)
H70.648−0.02810.0040.032*
C80.3299 (7)0.0625 (5)−0.0887 (4)0.0259 (9)
H8A0.37620.1478−0.13880.031*
H8B0.273−0.0127−0.16030.031*
C90.1701 (6)0.0969 (4)0.0167 (4)0.0233 (9)
H90.02040.1361−0.02750.028*
C100.1710 (7)−0.0459 (4)0.0960 (4)0.0256 (9)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
O10.0249 (14)0.0180 (14)0.0299 (14)−0.0012 (12)0.0044 (12)−0.0053 (12)
O20.0234 (14)0.0253 (16)0.0352 (16)0.0018 (13)0.0050 (12)−0.0054 (13)
O30.0253 (15)0.0189 (14)0.0349 (16)−0.0018 (13)0.0067 (12)0.0007 (13)
O40.0344 (17)0.0263 (16)0.0359 (16)−0.0089 (14)0.0091 (13)0.0022 (14)
N10.0215 (17)0.0192 (17)0.0275 (18)0.0024 (14)0.0017 (14)−0.0023 (15)
C10.027 (2)0.018 (2)0.031 (2)0.0018 (17)0.0092 (17)−0.0050 (17)
C20.034 (2)0.018 (2)0.039 (2)0.0029 (18)0.0049 (19)−0.0017 (19)
C30.037 (2)0.023 (2)0.035 (2)−0.0045 (18)0.0101 (19)−0.0047 (19)
C40.026 (2)0.020 (2)0.034 (2)−0.0009 (17)0.0064 (17)−0.0039 (18)
C50.023 (2)0.0157 (19)0.029 (2)−0.0012 (16)0.0028 (16)0.0015 (16)
C60.024 (2)0.021 (2)0.030 (2)−0.0009 (17)0.0057 (16)−0.0024 (17)
C70.028 (2)0.022 (2)0.030 (2)−0.0006 (18)0.0099 (19)−0.0045 (18)
C80.031 (2)0.019 (2)0.028 (2)−0.0005 (17)0.0056 (17)−0.0007 (18)
C90.0238 (19)0.0187 (19)0.027 (2)−0.0022 (17)0.0049 (17)−0.0039 (16)
C100.031 (2)0.020 (2)0.025 (2)−0.0038 (18)0.0024 (17)−0.0047 (17)

Geometric parameters (Å, °)

O1—C51.359 (5)C3—H3B0.98
O1—C11.484 (5)C3—H3C0.98
O2—C51.215 (5)C4—H4A0.98
O3—C101.377 (5)C4—H4B0.98
O3—C71.475 (5)C4—H4C0.98
O4—C101.196 (5)C6—C71.526 (6)
N1—C51.353 (5)C6—H6A0.99
N1—C91.478 (5)C6—H6B0.99
N1—C61.481 (5)C7—C81.529 (6)
C1—C41.516 (5)C7—H71
C1—C31.516 (6)C8—C91.528 (6)
C1—C21.524 (6)C8—H8A0.99
C2—H2A0.98C8—H8B0.99
C2—H2B0.98C9—C101.528 (6)
C2—H2C0.98C9—H91
C3—H3A0.98
C5—O1—C1120.7 (3)O2—C5—O1126.3 (4)
C10—O3—C7106.3 (3)N1—C5—O1109.0 (3)
C5—N1—C9122.1 (3)N1—C6—C799.4 (3)
C5—N1—C6127.1 (3)N1—C6—H6A111.9
C9—N1—C6108.3 (3)C7—C6—H6A111.9
O1—C1—C4101.8 (3)N1—C6—H6B111.9
O1—C1—C3110.0 (3)C7—C6—H6B111.9
C4—C1—C3111.5 (4)H6A—C6—H6B109.6
O1—C1—C2110.3 (3)O3—C7—C6106.4 (3)
C4—C1—C2110.7 (3)O3—C7—C8102.2 (3)
C3—C1—C2112.0 (3)C6—C7—C8102.7 (3)
C1—C2—H2A109.5O3—C7—H7114.7
C1—C2—H2B109.5C6—C7—H7114.7
H2A—C2—H2B109.5C8—C7—H7114.7
C1—C2—H2C109.5C9—C8—C791.9 (3)
H2A—C2—H2C109.5C9—C8—H8A113.3
H2B—C2—H2C109.5C7—C8—H8A113.3
C1—C3—H3A109.5C9—C8—H8B113.3
C1—C3—H3B109.5C7—C8—H8B113.3
H3A—C3—H3B109.5H8A—C8—H8B110.6
C1—C3—H3C109.5N1—C9—C10103.9 (3)
H3A—C3—H3C109.5N1—C9—C8100.6 (3)
H3B—C3—H3C109.5C10—C9—C8100.1 (3)
C1—C4—H4A109.5N1—C9—H9116.5
C1—C4—H4B109.5C10—C9—H9116.5
H4A—C4—H4B109.5C8—C9—H9116.5
C1—C4—H4C109.5O4—C10—O3122.4 (4)
H4A—C4—H4C109.5O4—C10—C9132.2 (4)
H4B—C4—H4C109.5O3—C10—C9105.4 (3)
O2—C5—N1124.7 (4)
C5—O1—C1—C4−178.9 (3)O3—C7—C8—C953.1 (3)
C5—O1—C1—C362.7 (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—C1069.1 (4)
C6—N1—C5—O2−169.3 (4)C5—N1—C9—C8162.7 (3)
C9—N1—C5—O1171.3 (3)C6—N1—C9—C8−34.2 (4)
C6—N1—C5—O111.6 (5)C7—C8—C9—N153.9 (3)
C1—O1—C5—O20.9 (6)C7—C8—C9—C10−52.5 (3)
C1—O1—C5—N1179.9 (3)C7—O3—C10—O4−178.8 (4)
C5—N1—C6—C7159.9 (4)C7—O3—C10—C9−1.3 (4)
C9—N1—C6—C7−2.1 (4)N1—C9—C10—O4109.5 (5)
C10—O3—C7—C673.2 (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—O336.1 (4)
N1—C6—C7—C838.0 (4)

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: WW2125).

References

  • Allen, F. H. (2002). Acta Cryst. B58, 380–388. [PubMed]
  • Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst.27, 435.
  • Didier, C., Crichter, D. J., Walshe, N. D., Kojima, Y., Yamauchi, Y. & Barrett, A. G. M. (2004). J. Org. Chem.69, 7875–7879. [PubMed]
  • Farrugia, L. J. (1997). J. Appl. Cryst.30, 565.
  • Farrugia, L. J. (1999). J. Appl. Cryst.32, 837–838.
  • Flack, H. D. & Schwarzenbach, D. (1988). Acta Cryst. A44, 499–506.
  • Gómez-Vidal, J. A. & Silverman, R. B. (2001). Org. Lett.3, 2481–2484. [PubMed]
  • Lenstra, A. T. H., Petit, G. H. & Geise, H. J. (1979). Cryst. Struct. Commun.8, 1023–1029.
  • Nonius (1998). COLLECT Nonius BV, Delft, The Netherlands.
  • Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
  • Papaioannou, D., Stavropoulos, G., Nastopoulos, V., Voliotis, S. & Leban, I. (1989). Acta Cryst. C45, 1651–1652.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]

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