organic compounds
(2S,4S)-3-Benzoyl-4-benzyl-2-tert-butyl-1,3-oxazolidin-5-one
aSchool of Chemistry, The University of Sydney, NSW 2006, Australia, and bSchool of Chemistry and Chemical Biology, University College Dublin, Belfield, Dublin 4, Ireland
*Correspondence e-mail: peter.rutledge@sydney.edu.au
In the title compound, C21H23NO3, the central oxazolidinone ring is approximately planar, the maximum deviation from the plane through the central ring being 0.043 (1) Å. The tert-butyl and benzyl substituents are cis to each other and trans to the N-benzoyl group. The interplanar angle between the aromatic rings of the C-benzyl and N-benzoyl groups is 81.10 (4)°.
Related literature
For background to this class of compound, see: Seebach & Naef (1981); Seebach et al. (1984); Seebach & Fadel (1985). For applications of these compounds in see: Krall et al. (2005); Barry & Rutledge (2008); Dungan et al. (2010, 2012). For related structures, see: Dungan et al. (2010); Barry et al. (2012).
Experimental
Crystal data
|
Data collection: SMART (Bruker, 2001); cell SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.
Supporting information
10.1107/S1600536812035556/kj2203sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812035556/kj2203Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812035556/kj2203Isup3.cdx
Supporting information file. DOI: 10.1107/S1600536812035556/kj2203Isup4.mol
Supporting information file. DOI: 10.1107/S1600536812035556/kj2203Isup5.cml
The title compound was prepared following the procedure reported by Seebach (Seebach & Fadel, 1985). Thus the sodium salt of L-phenylalanine was condensed with pivalaldehyde, by heating at reflux in pentane overnight under Dean-Stark conditions to affect azeotropic removal of water. The intermediate Schiff base thus formed was treated with benzoyl chloride in dichloromethane at 233 K, prompting
to give the crude product. Recrystallization from methanol gave white needles in a low overall yield (31%).A floating origin restraint was automatically generated by SHELXL. Hydrogen atoms were added at calculated positions and refined using a riding model. Their isotropic displacement parameters were fixed to 1.2 (1.5 for methyl groups) times the equivalent one of the parent atom. C—H bond lengths range from 0.95 Å to 1.00 Å.
Data collection: SMART (Bruker, 2001); cell
SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).View of (2S,4S)-3-benzoyl-4-benzyl-2-(tert-butyl)oxazolidin-5-one showing displacement ellipsoids at the 50% probability level. Note the cis arrangement of the tert-butyl and benzyl groups. |
C21H23NO3 | F(000) = 720 |
Mr = 337.40 | Dx = 1.222 Mg m−3 |
Monoclinic, C2 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: C 2y | Cell parameters from 9756 reflections |
a = 23.6627 (17) Å | θ = 3.0–28.4° |
b = 7.1449 (5) Å | µ = 0.08 mm−1 |
c = 12.2265 (9) Å | T = 100 K |
β = 117.470 (1)° | Rod, colourless |
V = 1834.0 (2) Å3 | 0.50 × 0.10 × 0.10 mm |
Z = 4 |
Bruker D8 platform diffractometer SMART APEX CCD area detector | 2390 independent reflections |
Radiation source: sealed tube | 2335 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
Detector resolution: 8.366 pixels mm-1 | θmax = 28.5°, θmin = 1.9° |
ϕ and ω scans | h = −31→31 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | k = −9→9 |
Tmin = 0.886, Tmax = 0.992 | l = −16→16 |
15833 measured reflections |
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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.05 | w = 1/[σ2(Fo2) + (0.0619P)2 + 0.4977P] where P = (Fo2 + 2Fc2)/3 |
2390 reflections | (Δ/σ)max = 0.005 |
229 parameters | Δρmax = 0.32 e Å−3 |
1 restraint | Δρmin = −0.19 e Å−3 |
C21H23NO3 | V = 1834.0 (2) Å3 |
Mr = 337.40 | Z = 4 |
Monoclinic, C2 | Mo Kα radiation |
a = 23.6627 (17) Å | µ = 0.08 mm−1 |
b = 7.1449 (5) Å | T = 100 K |
c = 12.2265 (9) Å | 0.50 × 0.10 × 0.10 mm |
β = 117.470 (1)° |
Bruker D8 platform diffractometer SMART APEX CCD area detector | 2390 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2000) | 2335 reflections with I > 2σ(I) |
Tmin = 0.886, Tmax = 0.992 | Rint = 0.019 |
15833 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 1 restraint |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.32 e Å−3 |
2390 reflections | Δρmin = −0.19 e Å−3 |
229 parameters |
Experimental. R(int) for selected reflections was 0.037 before and 0.019 after correction for absorption. The Ratio of minimum to maximum transmission is 0.893567. The λ/2 correction factor is 0.0015. Friedel pairs were merged. |
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 | ||
C1 | 0.32528 (7) | 0.0666 (2) | 0.72715 (13) | 0.0201 (3) | |
H1 | 0.2936 | 0.1615 | 0.6991 | 0.024* | |
C2 | 0.35910 (8) | 0.0255 (3) | 0.85255 (14) | 0.0238 (3) | |
H2 | 0.3504 | 0.0929 | 0.9101 | 0.029* | |
C3 | 0.40519 (8) | −0.1129 (3) | 0.89347 (14) | 0.0269 (4) | |
H3 | 0.4285 | −0.1390 | 0.9791 | 0.032* | |
C4 | 0.41737 (8) | −0.2135 (3) | 0.80964 (16) | 0.0274 (3) | |
H4 | 0.4485 | −0.3100 | 0.8379 | 0.033* | |
C5 | 0.38402 (7) | −0.1736 (2) | 0.68398 (15) | 0.0232 (3) | |
H5 | 0.3924 | −0.2422 | 0.6265 | 0.028* | |
C6 | 0.33832 (7) | −0.0322 (2) | 0.64354 (13) | 0.0174 (3) | |
C7 | 0.29922 (7) | 0.0067 (2) | 0.50761 (13) | 0.0168 (3) | |
O1 | 0.24806 (5) | −0.06990 (19) | 0.44701 (10) | 0.0243 (3) | |
N | 0.32549 (6) | 0.12804 (19) | 0.45687 (11) | 0.0160 (3) | |
C8 | 0.28720 (7) | 0.1929 (2) | 0.32915 (13) | 0.0167 (3) | |
H8 | 0.2410 | 0.1878 | 0.3077 | 0.020* | |
C9 | 0.29772 (7) | 0.0885 (2) | 0.22984 (13) | 0.0186 (3) | |
C10 | 0.36825 (7) | 0.0743 (3) | 0.26437 (15) | 0.0248 (3) | |
H10A | 0.3731 | 0.0156 | 0.1967 | 0.037* | |
H10B | 0.3901 | −0.0016 | 0.3391 | 0.037* | |
H10C | 0.3870 | 0.2000 | 0.2795 | 0.037* | |
C11 | 0.26947 (8) | −0.1078 (2) | 0.21368 (14) | 0.0240 (3) | |
H11A | 0.2922 | −0.1782 | 0.2906 | 0.036* | |
H11B | 0.2738 | −0.1725 | 0.1472 | 0.036* | |
H11C | 0.2243 | −0.0989 | 0.1928 | 0.036* | |
C12 | 0.26277 (8) | 0.1979 (3) | 0.10837 (14) | 0.0269 (3) | |
H12A | 0.2636 | 0.1257 | 0.0410 | 0.040* | |
H12B | 0.2840 | 0.3185 | 0.1158 | 0.040* | |
H12C | 0.2185 | 0.2193 | 0.0910 | 0.040* | |
O2 | 0.30612 (5) | 0.38597 (16) | 0.33203 (9) | 0.0201 (2) | |
C13 | 0.35521 (7) | 0.4321 (2) | 0.44092 (13) | 0.0182 (3) | |
O3 | 0.38072 (5) | 0.58182 (17) | 0.45787 (10) | 0.0239 (2) | |
C14 | 0.37239 (6) | 0.2706 (2) | 0.53073 (12) | 0.0155 (3) | |
H14 | 0.3649 | 0.3077 | 0.6019 | 0.019* | |
C15 | 0.44249 (6) | 0.2112 (2) | 0.57882 (13) | 0.0179 (3) | |
H15A | 0.4465 | 0.0764 | 0.5999 | 0.022* | |
H15B | 0.4547 | 0.2281 | 0.5121 | 0.022* | |
C16 | 0.48839 (6) | 0.3203 (2) | 0.69091 (13) | 0.0171 (3) | |
C17 | 0.49970 (7) | 0.2615 (3) | 0.80782 (14) | 0.0239 (3) | |
H17 | 0.4764 | 0.1590 | 0.8162 | 0.029* | |
C18 | 0.54481 (8) | 0.3517 (3) | 0.91234 (15) | 0.0301 (4) | |
H18 | 0.5519 | 0.3112 | 0.9917 | 0.036* | |
C19 | 0.57940 (8) | 0.4999 (3) | 0.90157 (15) | 0.0296 (4) | |
H19 | 0.6111 | 0.5588 | 0.9733 | 0.035* | |
C20 | 0.56771 (8) | 0.5622 (3) | 0.78598 (16) | 0.0293 (4) | |
H20 | 0.5910 | 0.6653 | 0.7782 | 0.035* | |
C21 | 0.52189 (7) | 0.4739 (2) | 0.68114 (14) | 0.0224 (3) | |
H21 | 0.5134 | 0.5190 | 0.6019 | 0.027* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0200 (6) | 0.0198 (7) | 0.0207 (7) | 0.0012 (6) | 0.0096 (5) | 0.0004 (6) |
C2 | 0.0277 (8) | 0.0263 (8) | 0.0187 (7) | −0.0026 (6) | 0.0117 (6) | −0.0014 (6) |
C3 | 0.0270 (8) | 0.0269 (8) | 0.0213 (7) | −0.0038 (7) | 0.0064 (6) | 0.0055 (6) |
C4 | 0.0262 (8) | 0.0199 (8) | 0.0313 (8) | 0.0045 (6) | 0.0093 (7) | 0.0049 (7) |
C5 | 0.0244 (7) | 0.0191 (7) | 0.0261 (7) | 0.0007 (6) | 0.0116 (6) | −0.0032 (6) |
C6 | 0.0169 (6) | 0.0178 (7) | 0.0176 (6) | −0.0037 (6) | 0.0079 (5) | −0.0013 (5) |
C7 | 0.0169 (6) | 0.0185 (7) | 0.0164 (6) | −0.0011 (5) | 0.0090 (5) | −0.0030 (5) |
O1 | 0.0211 (5) | 0.0310 (7) | 0.0206 (5) | −0.0092 (5) | 0.0095 (4) | −0.0036 (5) |
N | 0.0146 (5) | 0.0178 (6) | 0.0139 (5) | −0.0020 (5) | 0.0051 (5) | −0.0030 (5) |
C8 | 0.0157 (6) | 0.0170 (7) | 0.0154 (6) | −0.0014 (5) | 0.0054 (5) | −0.0011 (5) |
C9 | 0.0220 (7) | 0.0187 (7) | 0.0145 (6) | −0.0045 (6) | 0.0079 (5) | −0.0022 (5) |
C10 | 0.0254 (7) | 0.0278 (8) | 0.0247 (7) | −0.0024 (7) | 0.0145 (6) | −0.0062 (7) |
C11 | 0.0326 (8) | 0.0205 (8) | 0.0195 (6) | −0.0074 (7) | 0.0124 (6) | −0.0042 (6) |
C12 | 0.0348 (8) | 0.0257 (8) | 0.0169 (7) | −0.0033 (7) | 0.0092 (6) | 0.0023 (6) |
O2 | 0.0205 (5) | 0.0164 (5) | 0.0197 (5) | −0.0009 (4) | 0.0062 (4) | −0.0005 (4) |
C13 | 0.0166 (6) | 0.0181 (7) | 0.0202 (6) | 0.0016 (6) | 0.0087 (5) | −0.0024 (6) |
O3 | 0.0274 (6) | 0.0173 (5) | 0.0259 (5) | −0.0038 (5) | 0.0113 (5) | −0.0034 (5) |
C14 | 0.0139 (6) | 0.0156 (6) | 0.0165 (6) | −0.0024 (5) | 0.0065 (5) | −0.0036 (5) |
C15 | 0.0139 (6) | 0.0188 (7) | 0.0199 (6) | −0.0013 (6) | 0.0068 (5) | −0.0036 (6) |
C16 | 0.0126 (6) | 0.0189 (7) | 0.0188 (6) | 0.0008 (5) | 0.0065 (5) | −0.0024 (6) |
C17 | 0.0189 (7) | 0.0296 (8) | 0.0223 (7) | 0.0001 (6) | 0.0087 (6) | 0.0039 (7) |
C18 | 0.0253 (7) | 0.0419 (11) | 0.0186 (7) | 0.0069 (8) | 0.0062 (6) | 0.0013 (7) |
C19 | 0.0207 (7) | 0.0327 (9) | 0.0250 (7) | 0.0024 (7) | 0.0017 (6) | −0.0119 (7) |
C20 | 0.0247 (8) | 0.0241 (8) | 0.0350 (9) | −0.0071 (7) | 0.0103 (7) | −0.0082 (8) |
C21 | 0.0225 (7) | 0.0222 (8) | 0.0227 (7) | −0.0037 (6) | 0.0105 (6) | −0.0022 (6) |
C1—C6 | 1.389 (2) | C11—H11A | 0.9800 |
C1—C2 | 1.395 (2) | C11—H11B | 0.9800 |
C1—H1 | 0.9500 | C11—H11C | 0.9800 |
C2—C3 | 1.384 (2) | C12—H12A | 0.9800 |
C2—H2 | 0.9500 | C12—H12B | 0.9800 |
C3—C4 | 1.387 (3) | C12—H12C | 0.9800 |
C3—H3 | 0.9500 | O2—C13 | 1.3431 (17) |
C4—C5 | 1.395 (2) | C13—O3 | 1.198 (2) |
C4—H4 | 0.9500 | C13—C14 | 1.514 (2) |
C5—C6 | 1.393 (2) | C14—C15 | 1.5418 (18) |
C5—H5 | 0.9500 | C14—H14 | 1.0000 |
C6—C7 | 1.5090 (19) | C15—C16 | 1.5141 (19) |
C7—O1 | 1.2194 (18) | C15—H15A | 0.9900 |
C7—N | 1.3706 (19) | C15—H15B | 0.9900 |
N—C14 | 1.4695 (18) | C16—C21 | 1.391 (2) |
N—C8 | 1.4728 (18) | C16—C17 | 1.392 (2) |
C8—O2 | 1.4455 (19) | C17—C18 | 1.389 (2) |
C8—C9 | 1.540 (2) | C17—H17 | 0.9500 |
C8—H8 | 1.0000 | C18—C19 | 1.381 (3) |
C9—C10 | 1.524 (2) | C18—H18 | 0.9500 |
C9—C11 | 1.527 (2) | C19—C20 | 1.383 (3) |
C9—C12 | 1.539 (2) | C19—H19 | 0.9500 |
C10—H10A | 0.9800 | C20—C21 | 1.391 (2) |
C10—H10B | 0.9800 | C20—H20 | 0.9500 |
C10—H10C | 0.9800 | C21—H21 | 0.9500 |
C6—C1—C2 | 119.49 (15) | H11A—C11—H11B | 109.5 |
C6—C1—H1 | 120.3 | C9—C11—H11C | 109.5 |
C2—C1—H1 | 120.3 | H11A—C11—H11C | 109.5 |
C3—C2—C1 | 120.32 (15) | H11B—C11—H11C | 109.5 |
C3—C2—H2 | 119.8 | C9—C12—H12A | 109.5 |
C1—C2—H2 | 119.8 | C9—C12—H12B | 109.5 |
C2—C3—C4 | 120.08 (14) | H12A—C12—H12B | 109.5 |
C2—C3—H3 | 120.0 | C9—C12—H12C | 109.5 |
C4—C3—H3 | 120.0 | H12A—C12—H12C | 109.5 |
C3—C4—C5 | 120.20 (15) | H12B—C12—H12C | 109.5 |
C3—C4—H4 | 119.9 | C13—O2—C8 | 112.03 (12) |
C5—C4—H4 | 119.9 | O3—C13—O2 | 121.81 (14) |
C6—C5—C4 | 119.44 (15) | O3—C13—C14 | 127.58 (14) |
C6—C5—H5 | 120.3 | O2—C13—C14 | 110.60 (13) |
C4—C5—H5 | 120.3 | N—C14—C13 | 102.04 (11) |
C1—C6—C5 | 120.46 (14) | N—C14—C15 | 114.74 (12) |
C1—C6—C7 | 119.02 (13) | C13—C14—C15 | 111.59 (12) |
C5—C6—C7 | 120.39 (13) | N—C14—H14 | 109.4 |
O1—C7—N | 122.64 (13) | C13—C14—H14 | 109.4 |
O1—C7—C6 | 121.26 (13) | C15—C14—H14 | 109.4 |
N—C7—C6 | 116.08 (12) | C16—C15—C14 | 113.58 (12) |
C7—N—C14 | 122.12 (12) | C16—C15—H15A | 108.9 |
C7—N—C8 | 119.56 (12) | C14—C15—H15A | 108.9 |
C14—N—C8 | 110.75 (12) | C16—C15—H15B | 108.9 |
O2—C8—N | 104.03 (11) | C14—C15—H15B | 108.9 |
O2—C8—C9 | 108.70 (12) | H15A—C15—H15B | 107.7 |
N—C8—C9 | 116.05 (12) | C21—C16—C17 | 118.63 (14) |
O2—C8—H8 | 109.3 | C21—C16—C15 | 121.86 (13) |
N—C8—H8 | 109.3 | C17—C16—C15 | 119.45 (14) |
C9—C8—H8 | 109.3 | C18—C17—C16 | 120.44 (16) |
C10—C9—C11 | 109.45 (14) | C18—C17—H17 | 119.8 |
C10—C9—C12 | 109.46 (13) | C16—C17—H17 | 119.8 |
C11—C9—C12 | 109.49 (12) | C19—C18—C17 | 120.37 (16) |
C10—C9—C8 | 111.61 (12) | C19—C18—H18 | 119.8 |
C11—C9—C8 | 109.08 (12) | C17—C18—H18 | 119.8 |
C12—C9—C8 | 107.72 (13) | C18—C19—C20 | 119.76 (16) |
C9—C10—H10A | 109.5 | C18—C19—H19 | 120.1 |
C9—C10—H10B | 109.5 | C20—C19—H19 | 120.1 |
H10A—C10—H10B | 109.5 | C19—C20—C21 | 119.95 (17) |
C9—C10—H10C | 109.5 | C19—C20—H20 | 120.0 |
H10A—C10—H10C | 109.5 | C21—C20—H20 | 120.0 |
H10B—C10—H10C | 109.5 | C16—C21—C20 | 120.78 (15) |
C9—C11—H11A | 109.5 | C16—C21—H21 | 119.6 |
C9—C11—H11B | 109.5 | C20—C21—H21 | 119.6 |
C6—C1—C2—C3 | −0.1 (2) | N—C8—C9—C12 | −170.29 (12) |
C1—C2—C3—C4 | −0.9 (3) | N—C8—O2—C13 | 7.13 (15) |
C2—C3—C4—C5 | 1.1 (3) | C9—C8—O2—C13 | −117.09 (13) |
C3—C4—C5—C6 | −0.2 (3) | C8—O2—C13—O3 | 174.27 (13) |
C2—C1—C6—C5 | 1.1 (2) | C8—O2—C13—C14 | −4.26 (16) |
C2—C1—C6—C7 | 177.00 (14) | C7—N—C14—C13 | −144.40 (13) |
C4—C5—C6—C1 | −0.9 (2) | C8—N—C14—C13 | 5.00 (14) |
C4—C5—C6—C7 | −176.77 (15) | C7—N—C14—C15 | 94.76 (16) |
C1—C6—C7—O1 | −84.5 (2) | C8—N—C14—C15 | −115.84 (13) |
C5—C6—C7—O1 | 91.41 (19) | O3—C13—C14—N | −178.96 (14) |
C1—C6—C7—N | 97.27 (16) | O2—C13—C14—N | −0.53 (15) |
C5—C6—C7—N | −86.80 (18) | O3—C13—C14—C15 | −56.0 (2) |
O1—C7—N—C14 | 156.59 (15) | O2—C13—C14—C15 | 122.48 (13) |
C6—C7—N—C14 | −25.2 (2) | N—C14—C15—C16 | −157.45 (12) |
O1—C7—N—C8 | 9.8 (2) | C13—C14—C15—C16 | 87.12 (15) |
C6—C7—N—C8 | −172.04 (13) | C14—C15—C16—C21 | −96.99 (16) |
C7—N—C8—O2 | 142.88 (12) | C14—C15—C16—C17 | 85.79 (17) |
C14—N—C8—O2 | −7.41 (14) | C21—C16—C17—C18 | −1.7 (2) |
C7—N—C8—C9 | −97.78 (16) | C15—C16—C17—C18 | 175.60 (15) |
C14—N—C8—C9 | 111.93 (13) | C16—C17—C18—C19 | −0.6 (3) |
O2—C8—C9—C10 | 66.66 (16) | C17—C18—C19—C20 | 1.9 (3) |
N—C8—C9—C10 | −50.11 (18) | C18—C19—C20—C21 | −0.9 (3) |
O2—C8—C9—C11 | −172.28 (12) | C17—C16—C21—C20 | 2.7 (2) |
N—C8—C9—C11 | 70.95 (15) | C15—C16—C21—C20 | −174.55 (15) |
O2—C8—C9—C12 | −53.52 (15) | C19—C20—C21—C16 | −1.4 (3) |
Experimental details
Crystal data | |
Chemical formula | C21H23NO3 |
Mr | 337.40 |
Crystal system, space group | Monoclinic, C2 |
Temperature (K) | 100 |
a, b, c (Å) | 23.6627 (17), 7.1449 (5), 12.2265 (9) |
β (°) | 117.470 (1) |
V (Å3) | 1834.0 (2) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.50 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Bruker D8 platform diffractometer SMART APEX CCD area detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2000) |
Tmin, Tmax | 0.886, 0.992 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 15833, 2390, 2335 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.672 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.088, 1.05 |
No. of reflections | 2390 |
No. of parameters | 229 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.19 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).
Acknowledgements
This work was supported by the University of Sydney and by the School of Chemistry and Chemical Biology and the Centre for Synthesis & Chemical Biology at University College Dublin under the Programme for Research in Third Level Institutions (PRTLI) administered by the HEA.
References
Barry, S. M., Mueller-Bunz, H. & Rutledge, P. J. (2012). Org. Biomol. Chem. doi: 10.1039/C2OB25834J. Google Scholar
Barry, S. M. & Rutledge, P. J. (2008). Synlett, pp. 2172–2174. Google Scholar
Bruker (2001). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Dungan, V. J., Ortin, Y., Mueller-Bunz, H. & Rutledge, P. J. (2010). Org. Biomol. Chem. 8, 1666–1673. Web of Science CSD CrossRef CAS PubMed Google Scholar
Dungan, V. J., Wong, S. M., Barry, S. M. & Rutledge, P. J. (2012). Tetrahedron, 68, 3231–3236. Web of Science CrossRef CAS Google Scholar
Krall, J. A., Rutledge, P. J. & Baldwin, J. E. (2005). Tetrahedron, 61, 137–143. Web of Science CrossRef CAS Google Scholar
Seebach, D. & Fadel, A. (1985). Helv. Chim. Acta, 68, 1243–1250. CrossRef CAS Web of Science Google Scholar
Seebach, D. & Naef, R. (1981). Helv. Chim. Acta, 64, 2704–2708. CrossRef CAS Web of Science Google Scholar
Seebach, D., Naef, R. & Calderari, G. (1984). Tetrahedron, 40, 1313–1324. CrossRef Web of Science Google Scholar
Sheldrick, G. M. (2000). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
The stucture of the title compound (2S,4S)-3-benzoyl-4-benzyl-2-(tert-butyl)oxazolidin-5-one is shown below (Fig. 1). This structure reveals that the oxazolidinone ring is approximately planar, with the tert-butyl and benzyl groups occupying the same face of the ring plane. Observation of the cis isomer is in accord with previously reported NMR experiments (Seebach & Fadel, 1985) and the crystal structures of related compounds (Dungan et al. 2010; Barry et al. 2012). In the crystal, the angle between the oxazolidinone ring and the phenyl ring of the N-benzoyl group (C1 to C6) is 65.74 (4)°, while the angle between the oxazolidinone and the phenyl ring of the C-benzyl group (C16 to C21) is 25.66 (7)°.
Oxazolidinones of this type are of interest due to their capacity to undergo stereoselective α-alkylation via the cyclic enolate, a reaction that exploits the principle of "self-reproduction of chirality centres" introduced by Seebach and co-workers (Seebach & Naef, 1981, Seebach et al., 1984, Seebach & Fadel, 1985). Thus the tert-butyl group directs an incoming electrophile to the opposite face of the planar enolate, giving an enantiopure product with retention of stereochemistry from the original oxazolidinone.
We have recently applied this strategy in the synthesis of ligand architectures designed to mimic the structure and function of non-heme iron enzymes (Krall et al. 2005, Barry & Rutledge, 2008, Dungan et al. 2010, Dungan et al. 2012, Barry et al. 2012)