Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807034733/wk2064sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807034733/wk2064Isup2.hkl |
CCDC reference: 657814
The 4-phenyl-butan-2-one (10 mmol) was added to a mixture of nitrosobenzene (1 mmol) and trans-4-tert-butyldimethylsiloxy-D-proline (30 mol %) in DMSO (4 ml). The reaction was quenched after 3 h of vigorous stirring at room temperature by addition of aqueous NH4Cl solution. After work up, the residue was purified by silica gel chromatography. Colorless crystals were obtained by slow evaporation in petroleum and ethyl acetate at room temperature.
The hydrogen atoms were generated geometrically (C—H = 0.93, 0.98, 0.97 or 0.96Å for phenyl, tertiary, methylene or methyl H atoms respectively, and N—H = 0.86 Å) were included in the refinement in the riding model approximation except the NH where all parameters were refined. The displacement parameters of methyl H atoms were set to 1.5 times Ueq of the equivalent isotropic displacement parameters of their parent atoms, while those of other CH atoms were set to 1.2 times. In the absence of significant anomalous scattering effects, Friedel pairs were merged. The absolute configuration was assumed from the synthesis.
Chiral α-hydroxy ketones (acyloins) are useful synthetic intermediates (Davis & Chen, 1992). In recent years, three groups have reported proline and proline analogue-catalyzed α-aminoxylation of ketones (Córdova et al., 2004; Hayashi et al., 2004; Momiyama et al., 2004), those compounds can be converted to acyloins. In our work of chiral acyloins, we obtain the title compound (I), and here report its crystal structure. In the crystal packing of (I), the carbonyl O atom is engaged in H-bonding with the N—H of the adjacent molecule.
For related literature, see: Córdova et al. (2004); Davis & Chen (1992); Farrugia (1997); Hayashi et al. (2004); Momiyama et al. (2004).
Data collection: SMART (Bruker, 2001); cell refinement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.
Fig. 1. ORTEPIII (Farrugia, 1997) plot of the title compound with displacement ellipsoids drawn at the 30% probability level. H atoms are drawn as spheres of arbitrary radii. |
C16H17NO2 | F(000) = 544 |
Mr = 255.31 | Dx = 1.184 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 756 reflections |
a = 5.5950 (17) Å | θ = 5.0–47.7° |
b = 15.847 (5) Å | µ = 0.08 mm−1 |
c = 16.156 (5) Å | T = 293 K |
V = 1432.4 (7) Å3 | Block, colourless |
Z = 4 | 0.48 × 0.18 × 0.09 mm |
Bruker APEX area-detector diffractometer | 1571 independent reflections |
Radiation source: fine-focus sealed tube | 781 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.148 |
φ scans | θmax = 25.5°, θmin = 1.8° |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | h = −6→6 |
Tmin = 0.751, Tmax = 1.000 | k = −19→17 |
7191 measured reflections | l = −19→16 |
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)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.145 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.85 | w = 1/[σ2(Fo2) + (0.0647P)2] where P = (Fo2 + 2Fc2)/3 |
1571 reflections | (Δ/σ)max < 0.001 |
178 parameters | Δρmax = 0.16 e Å−3 |
1 restraint | Δρmin = −0.21 e Å−3 |
C16H17NO2 | V = 1432.4 (7) Å3 |
Mr = 255.31 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 5.5950 (17) Å | µ = 0.08 mm−1 |
b = 15.847 (5) Å | T = 293 K |
c = 16.156 (5) Å | 0.48 × 0.18 × 0.09 mm |
Bruker APEX area-detector diffractometer | 1571 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2001) | 781 reflections with I > 2σ(I) |
Tmin = 0.751, Tmax = 1.000 | Rint = 0.148 |
7191 measured reflections |
R[F2 > 2σ(F2)] = 0.055 | 1 restraint |
wR(F2) = 0.145 | H atoms treated by a mixture of independent and constrained refinement |
S = 0.85 | Δρmax = 0.16 e Å−3 |
1571 reflections | Δρmin = −0.21 e Å−3 |
178 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 | 0.5061 (6) | 0.4253 (2) | 0.66177 (17) | 0.0762 (10) | |
O2 | 0.0167 (5) | 0.42246 (18) | 0.52562 (16) | 0.0597 (8) | |
N1 | −0.0743 (7) | 0.4977 (3) | 0.5659 (2) | 0.0633 (11) | |
C1 | 0.2625 (7) | 0.4174 (3) | 0.5431 (2) | 0.0510 (11) | |
H1 | 0.3403 | 0.4699 | 0.5255 | 0.061* | |
C2 | 0.3146 (9) | 0.4024 (3) | 0.6342 (3) | 0.0613 (12) | |
C3 | 0.1367 (10) | 0.3571 (3) | 0.6863 (3) | 0.0830 (15) | |
H3A | 0.0567 | 0.3153 | 0.6535 | 0.124* | |
H3B | 0.0217 | 0.3966 | 0.7073 | 0.124* | |
H3C | 0.2170 | 0.3302 | 0.7317 | 0.124* | |
C4 | 0.3649 (9) | 0.3440 (3) | 0.4935 (2) | 0.0645 (13) | |
H4A | 0.5313 | 0.3365 | 0.5086 | 0.077* | |
H4B | 0.2801 | 0.2929 | 0.5085 | 0.077* | |
C5 | 0.3484 (8) | 0.3561 (3) | 0.4006 (3) | 0.0536 (11) | |
C6 | 0.5259 (10) | 0.3996 (3) | 0.3615 (3) | 0.0810 (16) | |
H6 | 0.6546 | 0.4199 | 0.3921 | 0.097* | |
C7 | 0.5168 (12) | 0.4142 (3) | 0.2759 (3) | 0.0918 (18) | |
H7 | 0.6369 | 0.4449 | 0.2498 | 0.110* | |
C8 | 0.3291 (10) | 0.3827 (3) | 0.2312 (3) | 0.0778 (15) | |
H8 | 0.3218 | 0.3917 | 0.1744 | 0.093* | |
C9 | 0.1530 (10) | 0.3382 (3) | 0.2696 (3) | 0.0828 (16) | |
H9 | 0.0259 | 0.3166 | 0.2391 | 0.099* | |
C10 | 0.1640 (10) | 0.3252 (3) | 0.3547 (3) | 0.0723 (14) | |
H10 | 0.0433 | 0.2948 | 0.3806 | 0.087* | |
C11 | −0.1670 (8) | 0.5573 (3) | 0.5071 (3) | 0.0559 (11) | |
C12 | −0.0695 (9) | 0.5646 (3) | 0.4280 (3) | 0.0732 (15) | |
H12 | 0.0569 | 0.5306 | 0.4113 | 0.088* | |
C13 | −0.1665 (12) | 0.6238 (3) | 0.3757 (3) | 0.0846 (17) | |
H13 | −0.1084 | 0.6283 | 0.3219 | 0.101* | |
C14 | −0.3446 (12) | 0.6757 (3) | 0.4005 (4) | 0.0903 (18) | |
H14 | −0.4065 | 0.7156 | 0.3642 | 0.108* | |
C15 | −0.4343 (10) | 0.6694 (3) | 0.4799 (4) | 0.0843 (17) | |
H15 | −0.5564 | 0.7051 | 0.4972 | 0.101* | |
C16 | −0.3424 (9) | 0.6101 (3) | 0.5332 (3) | 0.0713 (13) | |
H16 | −0.4004 | 0.6062 | 0.5870 | 0.086* | |
H2 | −0.202 (6) | 0.480 (3) | 0.590 (3) | 0.083 (19)* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.064 (2) | 0.116 (3) | 0.0491 (18) | −0.007 (2) | −0.0015 (17) | 0.0073 (19) |
O2 | 0.0524 (18) | 0.0665 (19) | 0.0602 (18) | −0.0005 (17) | −0.0042 (16) | −0.0064 (16) |
N1 | 0.065 (3) | 0.077 (3) | 0.049 (2) | 0.010 (2) | −0.002 (2) | −0.006 (2) |
C1 | 0.051 (3) | 0.055 (3) | 0.047 (3) | 0.000 (2) | −0.005 (2) | 0.000 (2) |
C2 | 0.046 (3) | 0.083 (3) | 0.055 (3) | 0.002 (3) | 0.003 (2) | 0.003 (3) |
C3 | 0.085 (4) | 0.104 (4) | 0.060 (3) | −0.007 (4) | 0.006 (3) | 0.019 (3) |
C4 | 0.084 (3) | 0.059 (3) | 0.050 (3) | 0.008 (3) | −0.002 (3) | −0.001 (2) |
C5 | 0.053 (3) | 0.053 (2) | 0.055 (3) | 0.007 (3) | 0.008 (2) | 0.004 (2) |
C6 | 0.085 (4) | 0.093 (4) | 0.065 (3) | −0.012 (4) | 0.002 (3) | −0.012 (3) |
C7 | 0.104 (5) | 0.107 (4) | 0.065 (4) | −0.015 (4) | 0.011 (4) | 0.009 (3) |
C8 | 0.093 (4) | 0.085 (4) | 0.056 (3) | −0.007 (4) | −0.003 (3) | 0.003 (3) |
C9 | 0.090 (4) | 0.095 (4) | 0.063 (3) | −0.016 (4) | −0.014 (3) | 0.001 (3) |
C10 | 0.071 (3) | 0.083 (3) | 0.063 (3) | −0.011 (3) | −0.002 (3) | 0.009 (3) |
C11 | 0.053 (3) | 0.067 (3) | 0.048 (3) | 0.005 (3) | −0.003 (2) | −0.001 (2) |
C12 | 0.075 (4) | 0.094 (4) | 0.051 (3) | 0.004 (3) | 0.003 (3) | 0.008 (3) |
C13 | 0.104 (4) | 0.092 (4) | 0.058 (3) | 0.010 (4) | −0.003 (3) | 0.008 (3) |
C14 | 0.103 (5) | 0.079 (4) | 0.089 (5) | −0.006 (4) | −0.016 (4) | 0.016 (3) |
C15 | 0.080 (4) | 0.071 (3) | 0.102 (5) | 0.020 (3) | −0.002 (4) | −0.012 (3) |
C16 | 0.067 (3) | 0.079 (3) | 0.067 (3) | 0.010 (3) | 0.006 (3) | −0.011 (3) |
O1—C2 | 1.215 (5) | C7—C8 | 1.369 (7) |
O2—C1 | 1.406 (4) | C7—H7 | 0.9300 |
O2—N1 | 1.451 (5) | C8—C9 | 1.361 (7) |
N1—C11 | 1.436 (5) | C8—H8 | 0.9300 |
N1—H2 | 0.86 (2) | C9—C10 | 1.391 (7) |
C1—C2 | 1.519 (6) | C9—H9 | 0.9300 |
C1—C4 | 1.524 (5) | C10—H10 | 0.9300 |
C1—H1 | 0.9800 | C11—C16 | 1.357 (6) |
C2—C3 | 1.488 (6) | C11—C12 | 1.394 (6) |
C3—H3A | 0.9600 | C12—C13 | 1.374 (6) |
C3—H3B | 0.9600 | C12—H12 | 0.9300 |
C3—H3C | 0.9600 | C13—C14 | 1.353 (7) |
C4—C5 | 1.516 (6) | C13—H13 | 0.9300 |
C4—H4A | 0.9700 | C14—C15 | 1.380 (7) |
C4—H4B | 0.9700 | C14—H14 | 0.9300 |
C5—C10 | 1.362 (6) | C15—C16 | 1.374 (7) |
C5—C6 | 1.364 (6) | C15—H15 | 0.9300 |
C6—C7 | 1.404 (6) | C16—H16 | 0.9300 |
C6—H6 | 0.9300 | ||
C1—O2—N1 | 107.4 (3) | C8—C7—C6 | 119.2 (5) |
C11—N1—O2 | 111.7 (3) | C8—C7—H7 | 120.4 |
C11—N1—H2 | 103 (3) | C6—C7—H7 | 120.4 |
O2—N1—H2 | 103 (3) | C9—C8—C7 | 120.3 (5) |
O2—C1—C2 | 113.0 (3) | C9—C8—H8 | 119.9 |
O2—C1—C4 | 107.8 (3) | C7—C8—H8 | 119.9 |
C2—C1—C4 | 108.5 (4) | C8—C9—C10 | 119.7 (5) |
O2—C1—H1 | 109.1 | C8—C9—H9 | 120.2 |
C2—C1—H1 | 109.1 | C10—C9—H9 | 120.2 |
C4—C1—H1 | 109.1 | C5—C10—C9 | 121.2 (5) |
O1—C2—C3 | 121.7 (4) | C5—C10—H10 | 119.4 |
O1—C2—C1 | 118.5 (4) | C9—C10—H10 | 119.4 |
C3—C2—C1 | 119.7 (4) | C16—C11—C12 | 121.1 (5) |
C2—C3—H3A | 109.5 | C16—C11—N1 | 117.5 (4) |
C2—C3—H3B | 109.5 | C12—C11—N1 | 121.3 (4) |
H3A—C3—H3B | 109.5 | C13—C12—C11 | 117.8 (5) |
C2—C3—H3C | 109.5 | C13—C12—H12 | 121.1 |
H3A—C3—H3C | 109.5 | C11—C12—H12 | 121.1 |
H3B—C3—H3C | 109.5 | C14—C13—C12 | 121.5 (5) |
C5—C4—C1 | 113.7 (4) | C14—C13—H13 | 119.2 |
C5—C4—H4A | 108.8 | C12—C13—H13 | 119.2 |
C1—C4—H4A | 108.8 | C13—C14—C15 | 120.0 (5) |
C5—C4—H4B | 108.8 | C13—C14—H14 | 120.0 |
C1—C4—H4B | 108.8 | C15—C14—H14 | 120.0 |
H4A—C4—H4B | 107.7 | C16—C15—C14 | 119.6 (5) |
C10—C5—C6 | 118.8 (4) | C16—C15—H15 | 120.2 |
C10—C5—C4 | 122.7 (4) | C14—C15—H15 | 120.2 |
C6—C5—C4 | 118.5 (5) | C11—C16—C15 | 119.9 (5) |
C5—C6—C7 | 120.8 (5) | C11—C16—H16 | 120.0 |
C5—C6—H6 | 119.6 | C15—C16—H16 | 120.0 |
C7—C6—H6 | 119.6 | ||
C1—O2—N1—C11 | 117.7 (4) | C7—C8—C9—C10 | 0.3 (8) |
N1—O2—C1—C2 | 66.1 (5) | C6—C5—C10—C9 | −0.8 (7) |
N1—O2—C1—C4 | −174.0 (3) | C4—C5—C10—C9 | 179.3 (5) |
O2—C1—C2—O1 | −154.9 (4) | C8—C9—C10—C5 | −0.1 (8) |
C4—C1—C2—O1 | 85.6 (5) | O2—N1—C11—C16 | 152.2 (4) |
O2—C1—C2—C3 | 27.9 (6) | O2—N1—C11—C12 | −32.1 (6) |
C4—C1—C2—C3 | −91.6 (5) | C16—C11—C12—C13 | −3.7 (7) |
O2—C1—C4—C5 | 63.6 (5) | N1—C11—C12—C13 | −179.3 (4) |
C2—C1—C4—C5 | −173.7 (4) | C11—C12—C13—C14 | 2.5 (8) |
C1—C4—C5—C10 | −94.4 (5) | C12—C13—C14—C15 | −0.6 (8) |
C1—C4—C5—C6 | 85.7 (5) | C13—C14—C15—C16 | −0.2 (8) |
C10—C5—C6—C7 | 1.5 (7) | C12—C11—C16—C15 | 3.0 (7) |
C4—C5—C6—C7 | −178.6 (5) | N1—C11—C16—C15 | 178.8 (4) |
C5—C6—C7—C8 | −1.3 (8) | C14—C15—C16—C11 | −1.0 (7) |
C6—C7—C8—C9 | 0.4 (8) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H2···O1i | 0.86 (2) | 2.18 (2) | 3.038 (6) | 173 (4) |
Symmetry code: (i) x−1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C16H17NO2 |
Mr | 255.31 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 293 |
a, b, c (Å) | 5.5950 (17), 15.847 (5), 16.156 (5) |
V (Å3) | 1432.4 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.48 × 0.18 × 0.09 |
Data collection | |
Diffractometer | Bruker APEX area-detector |
Absorption correction | Multi-scan (SADABS; Bruker, 2001) |
Tmin, Tmax | 0.751, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7191, 1571, 781 |
Rint | 0.148 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.055, 0.145, 0.85 |
No. of reflections | 1571 |
No. of parameters | 178 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.16, −0.21 |
Computer programs: SMART (Bruker, 2001), SMART, SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H2···O1i | 0.86 (2) | 2.18 (2) | 3.038 (6) | 173 (4) |
Symmetry code: (i) x−1, y, z. |
Chiral α-hydroxy ketones (acyloins) are useful synthetic intermediates (Davis & Chen, 1992). In recent years, three groups have reported proline and proline analogue-catalyzed α-aminoxylation of ketones (Córdova et al., 2004; Hayashi et al., 2004; Momiyama et al., 2004), those compounds can be converted to acyloins. In our work of chiral acyloins, we obtain the title compound (I), and here report its crystal structure. In the crystal packing of (I), the carbonyl O atom is engaged in H-bonding with the N—H of the adjacent molecule.