organic compounds
tert-Butyl N-hydroxy-N-[(1S*,2R*)-2-(1-naphthyl)cyclopent-3-en-1-yl]carbamate
aDepartment of Chemistry, University of Toronto, Toronto, Ontario, Canada M5S 3H6, and bDepartment of Chemistry, University of Guelph, Guelph, Ontario, Canada N1G 2W1
*Correspondence e-mail: alough@chem.utoronto.ca
The relative stereochemistry of the title compound, C20H23NO3, was established by X-ray analysis. The contains two independent molecules. In the each type of molecule forms a centrosymmetric dimer via pairs of intermolecular O—H⋯O hydrogen bonds, resulting in an R22(10) loop in each case.
Experimental
Crystal data
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Refinement
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Data collection: COLLECT (Nonius, 2002); cell DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536809020315/hb2980sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809020315/hb2980Isup2.hkl
3-aza-2-oxabicyclo[2.2.1]hept-5-ene (I) (see Fig. 4) (99.4 mg, 0.504 mmol) and 1-napthalene boronic acid (103.1 mg, 0.599 mmol) were weighed into a dry vial and purged with nitrogen. Dried MeOH (2.3 ml) was measured out into a dry vial and purged with nitrogen. Inside an inert atmosphere (Ar) dry box, [Rh(COD)Cl]2 (15.6 mg, 0.031 mmol) and (±)-BINAP (41.0 mg, 0.066 mmol) were weighed out and dissolved in methanol (1.0 ml), and stirred for 30 minutes. NaHCO3 (85.4 mg, 1.03 mmol) was added to the vial containing the bicyclic alkene and dissolved in MeOH (1.3 ml) and transferred to the vial with the catalyst. The reaction was heated to 333 K and stirred overnight. The crude product was purified using
(EtOAc:hexanes = 1:4) to give (II) as the major stereoisomer as an off white solid (58.1 mg, 0.179 mmol, 36%). Colourless blocks of (I) were grown from a solution of the title compound in dichloromethane/hexanes.H atoms bonded to C atoms were placed in calculated positions with C—H = 0.95–1.00 and they were included in the
in a riding-model approximation with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl C atoms. H atoms bonded to O atoms were located in difference maps and refined independently with isotropic displacement parameters.Data collection: COLLECT (Nonius, 2002); cell
DENZO-SMN (Otwinowski & Minor, 1997); data reduction: DENZO-SMN (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C20H23NO3 | Z = 4 |
Mr = 325.39 | F(000) = 696 |
Triclinic, P1 | Dx = 1.258 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.4710 (5) Å | Cell parameters from 10769 reflections |
b = 8.4880 (4) Å | θ = 2.6–26.3° |
c = 26.1836 (12) Å | µ = 0.08 mm−1 |
α = 95.980 (3)° | T = 150 K |
β = 95.419 (2)° | Block, colourless |
γ = 111.960 (2)° | 0.22 × 0.18 × 0.14 mm |
V = 1718.32 (15) Å3 |
Nonius KappaCCD diffractometer | 6622 independent reflections |
Radiation source: fine-focus sealed tube | 4089 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.035 |
Detector resolution: 9 pixels mm-1 | θmax = 26.3°, θmin = 2.6° |
ϕ scans and ω scans with κ offsets | h = −10→10 |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | k = −10→10 |
Tmin = 0.918, Tmax = 0.989 | l = −32→30 |
10769 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.057 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.167 | w = 1/[σ2(Fo2) + (0.0652P)2 + 0.4209P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max < 0.001 |
6622 reflections | Δρmax = 0.33 e Å−3 |
448 parameters | Δρmin = −0.25 e Å−3 |
0 restraints | Extinction correction: SHELXTL (Version 6.1; Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0086 (16) |
C20H23NO3 | γ = 111.960 (2)° |
Mr = 325.39 | V = 1718.32 (15) Å3 |
Triclinic, P1 | Z = 4 |
a = 8.4710 (5) Å | Mo Kα radiation |
b = 8.4880 (4) Å | µ = 0.08 mm−1 |
c = 26.1836 (12) Å | T = 150 K |
α = 95.980 (3)° | 0.22 × 0.18 × 0.14 mm |
β = 95.419 (2)° |
Nonius KappaCCD diffractometer | 6622 independent reflections |
Absorption correction: multi-scan (SORTAV; Blessing, 1995) | 4089 reflections with I > 2σ(I) |
Tmin = 0.918, Tmax = 0.989 | Rint = 0.035 |
10769 measured reflections |
R[F2 > 2σ(F2)] = 0.057 | 0 restraints |
wR(F2) = 0.167 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.10 | Δρmax = 0.33 e Å−3 |
6622 reflections | Δρmin = −0.25 e Å−3 |
448 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 | ||
O1A | 0.6043 (2) | 0.4234 (3) | 0.45322 (7) | 0.0357 (5) | |
H1OA | 0.632 (5) | 0.537 (5) | 0.4709 (13) | 0.077 (12)* | |
O2A | 0.1728 (2) | 0.2277 (2) | 0.39933 (6) | 0.0282 (4) | |
O3A | 0.2995 (2) | 0.2761 (2) | 0.48346 (7) | 0.0330 (5) | |
N1A | 0.4517 (3) | 0.3873 (3) | 0.41951 (8) | 0.0286 (5) | |
C1A | 0.4750 (3) | 0.3877 (3) | 0.36519 (10) | 0.0284 (6) | |
H2 | 0.3603 | 0.3618 | 0.3446 | 0.034* | |
C2A | 0.5993 (4) | 0.5614 (4) | 0.35413 (11) | 0.0401 (7) | |
H3 | 0.5380 | 0.6363 | 0.3455 | 0.048* | |
H4 | 0.6908 | 0.6217 | 0.3840 | 0.048* | |
C3A | 0.6710 (4) | 0.5081 (4) | 0.30832 (11) | 0.0417 (7) | |
H3A | 0.7319 | 0.5847 | 0.2864 | 0.050* | |
C4A | 0.6395 (4) | 0.3422 (4) | 0.30201 (11) | 0.0396 (7) | |
H4A | 0.6735 | 0.2855 | 0.2745 | 0.047* | |
C5A | 0.5439 (3) | 0.2528 (3) | 0.34302 (10) | 0.0297 (6) | |
H5 | 0.6280 | 0.2422 | 0.3705 | 0.036* | |
C6A | 0.4023 (3) | 0.0765 (3) | 0.32410 (9) | 0.0286 (6) | |
C7A | 0.3103 (4) | 0.0433 (4) | 0.27530 (10) | 0.0326 (7) | |
H6 | 0.3390 | 0.1303 | 0.2537 | 0.039* | |
C8A | 0.1752 (4) | −0.1155 (4) | 0.25649 (10) | 0.0363 (7) | |
H7 | 0.1135 | −0.1342 | 0.2227 | 0.044* | |
C9A | 0.1323 (4) | −0.2427 (4) | 0.28649 (11) | 0.0367 (7) | |
H8 | 0.0412 | −0.3500 | 0.2733 | 0.044* | |
C10A | 0.2221 (3) | −0.2172 (3) | 0.33715 (10) | 0.0306 (6) | |
C11A | 0.1782 (4) | −0.3471 (4) | 0.36895 (11) | 0.0372 (7) | |
H11A | 0.0884 | −0.4553 | 0.3558 | 0.045* | |
C12A | 0.2619 (4) | −0.3208 (4) | 0.41804 (12) | 0.0406 (7) | |
H12A | 0.2302 | −0.4096 | 0.4389 | 0.049* | |
C13A | 0.3959 (4) | −0.1609 (4) | 0.43766 (11) | 0.0374 (7) | |
H13A | 0.4550 | −0.1427 | 0.4718 | 0.045* | |
C14A | 0.4416 (4) | −0.0323 (3) | 0.40817 (10) | 0.0312 (6) | |
H14A | 0.5312 | 0.0750 | 0.4223 | 0.037* | |
C15A | 0.3582 (3) | −0.0552 (3) | 0.35665 (9) | 0.0280 (6) | |
C16A | 0.3056 (3) | 0.2920 (3) | 0.43773 (10) | 0.0268 (6) | |
C17A | −0.0021 (3) | 0.1253 (3) | 0.40984 (9) | 0.0295 (6) | |
C18A | −0.1061 (4) | 0.0807 (4) | 0.35615 (10) | 0.0396 (7) | |
H18A | −0.0993 | 0.1866 | 0.3429 | 0.059* | |
H18B | −0.2264 | 0.0099 | 0.3581 | 0.059* | |
H18C | −0.0597 | 0.0167 | 0.3327 | 0.059* | |
C19A | −0.0044 (4) | −0.0364 (3) | 0.42982 (11) | 0.0375 (7) | |
H19A | 0.0770 | −0.0054 | 0.4619 | 0.056* | |
H19B | 0.0289 | −0.1049 | 0.4037 | 0.056* | |
H19C | −0.1204 | −0.1036 | 0.4367 | 0.056* | |
C20A | −0.0614 (4) | 0.2358 (4) | 0.44690 (11) | 0.0369 (7) | |
H20A | 0.0147 | 0.2710 | 0.4802 | 0.055* | |
H20B | −0.1794 | 0.1694 | 0.4524 | 0.055* | |
H20C | −0.0576 | 0.3381 | 0.4319 | 0.055* | |
O1B | 0.4907 (3) | 0.6687 (2) | 0.05737 (8) | 0.0385 (5) | |
H1OB | 0.557 (5) | 0.667 (5) | 0.0335 (13) | 0.071 (12)* | |
O2B | 0.3481 (2) | 0.2662 (2) | 0.09741 (6) | 0.0301 (4) | |
O3B | 0.3099 (2) | 0.3398 (2) | 0.01728 (7) | 0.0352 (5) | |
N1B | 0.4828 (3) | 0.5352 (3) | 0.08597 (8) | 0.0306 (5) | |
C1B | 0.5343 (3) | 0.5915 (3) | 0.14138 (10) | 0.0296 (6) | |
H10 | 0.5293 | 0.4885 | 0.1576 | 0.036* | |
C2B | 0.7184 (4) | 0.7273 (4) | 0.15626 (11) | 0.0381 (7) | |
H11 | 0.8036 | 0.6735 | 0.1596 | 0.046* | |
H12 | 0.7483 | 0.8080 | 0.1307 | 0.046* | |
C3B | 0.7070 (4) | 0.8157 (3) | 0.20804 (11) | 0.0380 (7) | |
H3B | 0.8040 | 0.8856 | 0.2328 | 0.046* | |
C4B | 0.5462 (4) | 0.7841 (3) | 0.21470 (11) | 0.0369 (7) | |
H13 | 0.5138 | 0.8284 | 0.2450 | 0.044* | |
C5B | 0.4195 (3) | 0.6695 (3) | 0.16871 (10) | 0.0310 (6) | |
H14 | 0.3883 | 0.7435 | 0.1457 | 0.037* | |
C6B | 0.2554 (3) | 0.5356 (3) | 0.18060 (10) | 0.0276 (6) | |
C7B | 0.2584 (4) | 0.4624 (4) | 0.22474 (10) | 0.0351 (7) | |
H15 | 0.3642 | 0.4970 | 0.2472 | 0.042* | |
C8B | 0.1108 (4) | 0.3382 (4) | 0.23788 (11) | 0.0394 (7) | |
H16 | 0.1174 | 0.2898 | 0.2687 | 0.047* | |
C9B | −0.0427 (4) | 0.2871 (4) | 0.20617 (11) | 0.0404 (7) | |
H17 | −0.1429 | 0.2046 | 0.2155 | 0.049* | |
C10B | −0.0543 (4) | 0.3553 (3) | 0.15974 (11) | 0.0349 (7) | |
C11B | −0.2113 (4) | 0.2982 (4) | 0.12554 (12) | 0.0440 (8) | |
H11B | −0.3122 | 0.2162 | 0.1348 | 0.053* | |
C12B | −0.2198 (4) | 0.3590 (4) | 0.07978 (12) | 0.0459 (8) | |
H12B | −0.3258 | 0.3179 | 0.0571 | 0.055* | |
C13B | −0.0730 (4) | 0.4820 (4) | 0.06591 (11) | 0.0422 (8) | |
H13B | −0.0803 | 0.5254 | 0.0341 | 0.051* | |
C14B | 0.0808 (4) | 0.5398 (4) | 0.09798 (10) | 0.0330 (7) | |
H14B | 0.1796 | 0.6218 | 0.0877 | 0.040* | |
C15B | 0.0967 (3) | 0.4806 (3) | 0.14624 (10) | 0.0292 (6) | |
C16B | 0.3713 (3) | 0.3763 (3) | 0.06313 (10) | 0.0286 (6) | |
C17B | 0.2321 (4) | 0.0831 (3) | 0.08300 (10) | 0.0312 (6) | |
C18B | 0.2446 (4) | 0.0185 (4) | 0.13454 (10) | 0.0426 (8) | |
H18D | 0.3636 | 0.0327 | 0.1454 | 0.064* | |
H18E | 0.1692 | −0.1034 | 0.1307 | 0.064* | |
H18F | 0.2091 | 0.0845 | 0.1608 | 0.064* | |
C19B | 0.0503 (4) | 0.0681 (4) | 0.06712 (11) | 0.0376 (7) | |
H19D | 0.0130 | 0.1225 | 0.0958 | 0.056* | |
H19E | −0.0263 | −0.0535 | 0.0585 | 0.056* | |
H19F | 0.0463 | 0.1255 | 0.0367 | 0.056* | |
C20B | 0.2987 (4) | −0.0052 (4) | 0.04207 (11) | 0.0381 (7) | |
H20D | 0.4169 | 0.0097 | 0.0546 | 0.057* | |
H20E | 0.2969 | 0.0455 | 0.0102 | 0.057* | |
H20F | 0.2255 | −0.1280 | 0.0349 | 0.057* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1A | 0.0266 (11) | 0.0377 (12) | 0.0348 (11) | 0.0093 (9) | −0.0081 (9) | −0.0052 (9) |
O2A | 0.0224 (10) | 0.0306 (10) | 0.0256 (9) | 0.0043 (8) | 0.0011 (8) | 0.0027 (8) |
O3A | 0.0349 (12) | 0.0330 (11) | 0.0258 (10) | 0.0084 (9) | 0.0014 (8) | 0.0020 (8) |
N1A | 0.0230 (13) | 0.0302 (12) | 0.0263 (11) | 0.0061 (10) | −0.0029 (10) | −0.0014 (9) |
C1A | 0.0262 (15) | 0.0256 (14) | 0.0287 (14) | 0.0057 (12) | 0.0013 (12) | 0.0023 (11) |
C2A | 0.0356 (18) | 0.0331 (16) | 0.0432 (17) | 0.0037 (14) | 0.0048 (14) | 0.0074 (13) |
C3A | 0.0304 (17) | 0.0429 (19) | 0.0475 (18) | 0.0056 (15) | 0.0090 (14) | 0.0191 (15) |
C4A | 0.0335 (17) | 0.051 (2) | 0.0355 (16) | 0.0153 (15) | 0.0111 (13) | 0.0087 (14) |
C5A | 0.0280 (15) | 0.0317 (15) | 0.0286 (14) | 0.0103 (13) | 0.0044 (12) | 0.0049 (12) |
C6A | 0.0297 (16) | 0.0320 (15) | 0.0264 (14) | 0.0150 (13) | 0.0065 (12) | 0.0003 (12) |
C7A | 0.0386 (17) | 0.0340 (16) | 0.0282 (14) | 0.0178 (14) | 0.0053 (13) | 0.0031 (12) |
C8A | 0.0387 (18) | 0.0415 (18) | 0.0286 (15) | 0.0192 (15) | −0.0006 (13) | −0.0048 (13) |
C9A | 0.0325 (17) | 0.0327 (16) | 0.0392 (16) | 0.0102 (14) | 0.0029 (13) | −0.0074 (13) |
C10A | 0.0328 (16) | 0.0265 (15) | 0.0338 (15) | 0.0138 (13) | 0.0059 (13) | 0.0002 (12) |
C11A | 0.0404 (18) | 0.0241 (15) | 0.0459 (18) | 0.0119 (14) | 0.0068 (15) | 0.0020 (13) |
C12A | 0.049 (2) | 0.0292 (16) | 0.0482 (18) | 0.0181 (15) | 0.0119 (16) | 0.0112 (14) |
C13A | 0.0421 (18) | 0.0396 (17) | 0.0337 (15) | 0.0205 (15) | 0.0026 (13) | 0.0037 (13) |
C14A | 0.0332 (16) | 0.0282 (15) | 0.0318 (15) | 0.0119 (13) | 0.0033 (12) | 0.0041 (12) |
C15A | 0.0291 (16) | 0.0304 (15) | 0.0282 (14) | 0.0156 (13) | 0.0068 (12) | 0.0018 (12) |
C16A | 0.0265 (15) | 0.0235 (14) | 0.0276 (15) | 0.0085 (12) | −0.0004 (12) | 0.0004 (11) |
C17A | 0.0230 (15) | 0.0308 (15) | 0.0284 (14) | 0.0042 (12) | 0.0030 (12) | 0.0020 (12) |
C18A | 0.0299 (17) | 0.0461 (18) | 0.0353 (16) | 0.0081 (14) | 0.0022 (13) | 0.0021 (14) |
C19A | 0.0388 (18) | 0.0296 (16) | 0.0397 (16) | 0.0078 (14) | 0.0090 (14) | 0.0035 (13) |
C20A | 0.0299 (16) | 0.0363 (16) | 0.0429 (16) | 0.0115 (14) | 0.0085 (13) | 0.0013 (13) |
O1B | 0.0491 (14) | 0.0319 (11) | 0.0389 (11) | 0.0159 (10) | 0.0155 (10) | 0.0143 (9) |
O2B | 0.0367 (11) | 0.0238 (10) | 0.0248 (9) | 0.0076 (9) | −0.0009 (8) | 0.0031 (8) |
O3B | 0.0370 (12) | 0.0413 (12) | 0.0261 (10) | 0.0137 (10) | 0.0046 (9) | 0.0057 (8) |
N1B | 0.0369 (14) | 0.0251 (12) | 0.0304 (12) | 0.0104 (11) | 0.0089 (11) | 0.0098 (10) |
C1B | 0.0288 (15) | 0.0280 (15) | 0.0300 (14) | 0.0089 (13) | 0.0053 (12) | 0.0023 (12) |
C2B | 0.0279 (16) | 0.0349 (16) | 0.0458 (17) | 0.0061 (13) | 0.0072 (13) | 0.0028 (14) |
C3B | 0.0324 (17) | 0.0270 (15) | 0.0453 (17) | 0.0044 (13) | 0.0003 (14) | −0.0021 (13) |
C4B | 0.0405 (19) | 0.0273 (15) | 0.0360 (16) | 0.0086 (14) | 0.0044 (14) | −0.0059 (12) |
C5B | 0.0291 (16) | 0.0257 (15) | 0.0374 (15) | 0.0097 (13) | 0.0050 (12) | 0.0040 (12) |
C6B | 0.0276 (15) | 0.0247 (14) | 0.0309 (14) | 0.0103 (12) | 0.0077 (12) | 0.0016 (11) |
C7B | 0.0342 (17) | 0.0375 (17) | 0.0350 (16) | 0.0154 (14) | 0.0082 (13) | 0.0032 (13) |
C8B | 0.046 (2) | 0.0403 (17) | 0.0395 (16) | 0.0207 (16) | 0.0191 (15) | 0.0131 (14) |
C9B | 0.0358 (18) | 0.0336 (17) | 0.0531 (19) | 0.0122 (14) | 0.0190 (16) | 0.0054 (14) |
C10B | 0.0296 (17) | 0.0305 (15) | 0.0434 (17) | 0.0112 (13) | 0.0093 (14) | −0.0013 (13) |
C11B | 0.0298 (17) | 0.0405 (18) | 0.058 (2) | 0.0112 (15) | 0.0101 (15) | −0.0036 (16) |
C12B | 0.0288 (18) | 0.053 (2) | 0.054 (2) | 0.0198 (16) | −0.0016 (15) | −0.0103 (17) |
C13B | 0.042 (2) | 0.0512 (19) | 0.0394 (17) | 0.0276 (17) | 0.0021 (15) | 0.0004 (15) |
C14B | 0.0312 (16) | 0.0338 (16) | 0.0363 (16) | 0.0154 (13) | 0.0066 (13) | 0.0031 (13) |
C15B | 0.0282 (16) | 0.0256 (14) | 0.0352 (15) | 0.0126 (13) | 0.0070 (12) | −0.0003 (12) |
C16B | 0.0302 (16) | 0.0331 (16) | 0.0249 (14) | 0.0143 (13) | 0.0068 (12) | 0.0054 (12) |
C17B | 0.0356 (17) | 0.0216 (14) | 0.0306 (14) | 0.0062 (13) | 0.0033 (12) | −0.0006 (11) |
C18B | 0.057 (2) | 0.0305 (16) | 0.0341 (16) | 0.0111 (15) | 0.0031 (15) | 0.0036 (13) |
C19B | 0.0315 (17) | 0.0350 (16) | 0.0384 (16) | 0.0064 (14) | 0.0063 (13) | −0.0050 (13) |
C20B | 0.0380 (18) | 0.0313 (16) | 0.0429 (16) | 0.0133 (14) | 0.0045 (14) | −0.0019 (13) |
O1A—N1A | 1.405 (3) | O1B—N1B | 1.407 (3) |
O1A—H1OA | 0.96 (4) | O1B—H1OB | 0.88 (3) |
O2A—C16A | 1.337 (3) | O2B—C16B | 1.337 (3) |
O2A—C17A | 1.480 (3) | O2B—C17B | 1.479 (3) |
O3A—C16A | 1.223 (3) | O3B—C16B | 1.222 (3) |
N1A—C16A | 1.363 (3) | N1B—C16B | 1.357 (3) |
N1A—C1A | 1.454 (3) | N1B—C1B | 1.450 (3) |
C1A—C2A | 1.534 (4) | C1B—C2B | 1.536 (4) |
C1A—C5A | 1.554 (3) | C1B—C5B | 1.553 (3) |
C1A—H2 | 1.0000 | C1B—H10 | 1.0000 |
C2A—C3A | 1.497 (4) | C2B—C3B | 1.509 (4) |
C2A—H3 | 0.9900 | C2B—H11 | 0.9900 |
C2A—H4 | 0.9900 | C2B—H12 | 0.9900 |
C3A—C4A | 1.321 (4) | C3B—C4B | 1.319 (4) |
C3A—H3A | 0.9500 | C3B—H3B | 0.9500 |
C4A—C5A | 1.503 (4) | C4B—C5B | 1.510 (4) |
C4A—H4A | 0.9500 | C4B—H13 | 0.9500 |
C5A—C6A | 1.521 (4) | C5B—C6B | 1.515 (4) |
C5A—H5 | 1.0000 | C5B—H14 | 1.0000 |
C6A—C7A | 1.375 (4) | C6B—C7B | 1.371 (4) |
C6A—C15A | 1.436 (4) | C6B—C15B | 1.431 (4) |
C7A—C8A | 1.404 (4) | C7B—C8B | 1.402 (4) |
C7A—H6 | 0.9500 | C7B—H15 | 0.9500 |
C8A—C9A | 1.361 (4) | C8B—C9B | 1.366 (4) |
C8A—H7 | 0.9500 | C8B—H16 | 0.9500 |
C9A—C10A | 1.418 (4) | C9B—C10B | 1.410 (4) |
C9A—H8 | 0.9500 | C9B—H17 | 0.9500 |
C10A—C11A | 1.411 (4) | C10B—C11B | 1.417 (4) |
C10A—C15A | 1.427 (4) | C10B—C15B | 1.428 (4) |
C11A—C12A | 1.362 (4) | C11B—C12B | 1.359 (4) |
C11A—H11A | 0.9500 | C11B—H11B | 0.9500 |
C12A—C13A | 1.409 (4) | C12B—C13B | 1.400 (4) |
C12A—H12A | 0.9500 | C12B—H12B | 0.9500 |
C13A—C14A | 1.362 (4) | C13B—C14B | 1.369 (4) |
C13A—H13A | 0.9500 | C13B—H13B | 0.9500 |
C14A—C15A | 1.421 (4) | C14B—C15B | 1.421 (4) |
C14A—H14A | 0.9500 | C14B—H14B | 0.9500 |
C17A—C19A | 1.513 (4) | C17B—C19B | 1.511 (4) |
C17A—C18A | 1.517 (4) | C17B—C20B | 1.514 (3) |
C17A—C20A | 1.526 (3) | C17B—C18B | 1.518 (4) |
C18A—H18A | 0.9800 | C18B—H18D | 0.9800 |
C18A—H18B | 0.9800 | C18B—H18E | 0.9800 |
C18A—H18C | 0.9800 | C18B—H18F | 0.9800 |
C19A—H19A | 0.9800 | C19B—H19D | 0.9800 |
C19A—H19B | 0.9800 | C19B—H19E | 0.9800 |
C19A—H19C | 0.9800 | C19B—H19F | 0.9800 |
C20A—H20A | 0.9800 | C20B—H20D | 0.9800 |
C20A—H20B | 0.9800 | C20B—H20E | 0.9800 |
C20A—H20C | 0.9800 | C20B—H20F | 0.9800 |
N1A—O1A—H1OA | 104 (2) | N1B—O1B—H1OB | 107 (2) |
C16A—O2A—C17A | 120.66 (19) | C16B—O2B—C17B | 121.51 (19) |
C16A—N1A—O1A | 114.3 (2) | C16B—N1B—O1B | 115.0 (2) |
C16A—N1A—C1A | 125.8 (2) | C16B—N1B—C1B | 125.7 (2) |
O1A—N1A—C1A | 113.7 (2) | O1B—N1B—C1B | 113.83 (19) |
N1A—C1A—C2A | 113.2 (2) | N1B—C1B—C2B | 114.0 (2) |
N1A—C1A—C5A | 114.6 (2) | N1B—C1B—C5B | 115.4 (2) |
C2A—C1A—C5A | 105.8 (2) | C2B—C1B—C5B | 105.2 (2) |
N1A—C1A—H2 | 107.7 | N1B—C1B—H10 | 107.3 |
C2A—C1A—H2 | 107.7 | C2B—C1B—H10 | 107.3 |
C5A—C1A—H2 | 107.7 | C5B—C1B—H10 | 107.3 |
C3A—C2A—C1A | 101.8 (2) | C3B—C2B—C1B | 101.4 (2) |
C3A—C2A—H3 | 111.4 | C3B—C2B—H11 | 111.5 |
C1A—C2A—H3 | 111.4 | C1B—C2B—H11 | 111.5 |
C3A—C2A—H4 | 111.4 | C3B—C2B—H12 | 111.5 |
C1A—C2A—H4 | 111.4 | C1B—C2B—H12 | 111.5 |
H3—C2A—H4 | 109.3 | H11—C2B—H12 | 109.3 |
C4A—C3A—C2A | 112.1 (3) | C4B—C3B—C2B | 111.8 (3) |
C4A—C3A—H3A | 124.0 | C4B—C3B—H3B | 124.1 |
C2A—C3A—H3A | 124.0 | C2B—C3B—H3B | 124.1 |
C3A—C4A—C5A | 112.6 (2) | C3B—C4B—C5B | 112.3 (2) |
C3A—C4A—H4A | 123.7 | C3B—C4B—H13 | 123.8 |
C5A—C4A—H4A | 123.7 | C5B—C4B—H13 | 123.8 |
C4A—C5A—C6A | 115.7 (2) | C4B—C5B—C6B | 116.6 (2) |
C4A—C5A—C1A | 100.6 (2) | C4B—C5B—C1B | 100.6 (2) |
C6A—C5A—C1A | 113.1 (2) | C6B—C5B—C1B | 113.5 (2) |
C4A—C5A—H5 | 109.0 | C4B—C5B—H14 | 108.6 |
C6A—C5A—H5 | 109.0 | C6B—C5B—H14 | 108.6 |
C1A—C5A—H5 | 109.0 | C1B—C5B—H14 | 108.6 |
C7A—C6A—C15A | 118.9 (2) | C7B—C6B—C15B | 118.8 (3) |
C7A—C6A—C5A | 119.6 (2) | C7B—C6B—C5B | 119.6 (2) |
C15A—C6A—C5A | 121.5 (2) | C15B—C6B—C5B | 121.6 (2) |
C6A—C7A—C8A | 121.9 (3) | C6B—C7B—C8B | 122.3 (3) |
C6A—C7A—H6 | 119.1 | C6B—C7B—H15 | 118.9 |
C8A—C7A—H6 | 119.1 | C8B—C7B—H15 | 118.9 |
C9A—C8A—C7A | 120.2 (3) | C9B—C8B—C7B | 119.8 (3) |
C9A—C8A—H7 | 119.9 | C9B—C8B—H16 | 120.1 |
C7A—C8A—H7 | 119.9 | C7B—C8B—H16 | 120.1 |
C8A—C9A—C10A | 120.8 (3) | C8B—C9B—C10B | 120.9 (3) |
C8A—C9A—H8 | 119.6 | C8B—C9B—H17 | 119.5 |
C10A—C9A—H8 | 119.6 | C10B—C9B—H17 | 119.5 |
C11A—C10A—C9A | 121.6 (3) | C9B—C10B—C11B | 121.4 (3) |
C11A—C10A—C15A | 119.3 (2) | C9B—C10B—C15B | 119.2 (3) |
C9A—C10A—C15A | 119.1 (2) | C11B—C10B—C15B | 119.4 (3) |
C12A—C11A—C10A | 121.4 (3) | C12B—C11B—C10B | 121.0 (3) |
C12A—C11A—H11A | 119.3 | C12B—C11B—H11B | 119.5 |
C10A—C11A—H11A | 119.3 | C10B—C11B—H11B | 119.5 |
C11A—C12A—C13A | 119.6 (3) | C11B—C12B—C13B | 120.3 (3) |
C11A—C12A—H12A | 120.2 | C11B—C12B—H12B | 119.8 |
C13A—C12A—H12A | 120.2 | C13B—C12B—H12B | 119.8 |
C14A—C13A—C12A | 120.7 (3) | C14B—C13B—C12B | 120.2 (3) |
C14A—C13A—H13A | 119.7 | C14B—C13B—H13B | 119.9 |
C12A—C13A—H13A | 119.7 | C12B—C13B—H13B | 119.9 |
C13A—C14A—C15A | 121.4 (3) | C13B—C14B—C15B | 121.8 (3) |
C13A—C14A—H14A | 119.3 | C13B—C14B—H14B | 119.1 |
C15A—C14A—H14A | 119.3 | C15B—C14B—H14B | 119.1 |
C14A—C15A—C10A | 117.6 (2) | C14B—C15B—C10B | 117.2 (3) |
C14A—C15A—C6A | 123.3 (2) | C14B—C15B—C6B | 123.6 (3) |
C10A—C15A—C6A | 119.1 (2) | C10B—C15B—C6B | 119.1 (2) |
O3A—C16A—O2A | 126.1 (2) | O3B—C16B—O2B | 125.9 (2) |
O3A—C16A—N1A | 123.3 (2) | O3B—C16B—N1B | 124.1 (2) |
O2A—C16A—N1A | 110.4 (2) | O2B—C16B—N1B | 109.9 (2) |
O2A—C17A—C19A | 109.8 (2) | O2B—C17B—C19B | 109.9 (2) |
O2A—C17A—C18A | 101.86 (19) | O2B—C17B—C20B | 110.5 (2) |
C19A—C17A—C18A | 110.2 (2) | C19B—C17B—C20B | 113.5 (2) |
O2A—C17A—C20A | 109.7 (2) | O2B—C17B—C18B | 100.9 (2) |
C19A—C17A—C20A | 113.1 (2) | C19B—C17B—C18B | 109.6 (2) |
C18A—C17A—C20A | 111.5 (2) | C20B—C17B—C18B | 111.6 (2) |
C17A—C18A—H18A | 109.5 | C17B—C18B—H18D | 109.5 |
C17A—C18A—H18B | 109.5 | C17B—C18B—H18E | 109.5 |
H18A—C18A—H18B | 109.5 | H18D—C18B—H18E | 109.5 |
C17A—C18A—H18C | 109.5 | C17B—C18B—H18F | 109.5 |
H18A—C18A—H18C | 109.5 | H18D—C18B—H18F | 109.5 |
H18B—C18A—H18C | 109.5 | H18E—C18B—H18F | 109.5 |
C17A—C19A—H19A | 109.5 | C17B—C19B—H19D | 109.5 |
C17A—C19A—H19B | 109.5 | C17B—C19B—H19E | 109.5 |
H19A—C19A—H19B | 109.5 | H19D—C19B—H19E | 109.5 |
C17A—C19A—H19C | 109.5 | C17B—C19B—H19F | 109.5 |
H19A—C19A—H19C | 109.5 | H19D—C19B—H19F | 109.5 |
H19B—C19A—H19C | 109.5 | H19E—C19B—H19F | 109.5 |
C17A—C20A—H20A | 109.5 | C17B—C20B—H20D | 109.5 |
C17A—C20A—H20B | 109.5 | C17B—C20B—H20E | 109.5 |
H20A—C20A—H20B | 109.5 | H20D—C20B—H20E | 109.5 |
C17A—C20A—H20C | 109.5 | C17B—C20B—H20F | 109.5 |
H20A—C20A—H20C | 109.5 | H20D—C20B—H20F | 109.5 |
H20B—C20A—H20C | 109.5 | H20E—C20B—H20F | 109.5 |
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1OA···O3Ai | 0.96 (4) | 1.75 (4) | 2.689 (3) | 165 (3) |
O1B—H1OB···O3Bii | 0.88 (3) | 1.84 (4) | 2.714 (3) | 179 (4) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C20H23NO3 |
Mr | 325.39 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 150 |
a, b, c (Å) | 8.4710 (5), 8.4880 (4), 26.1836 (12) |
α, β, γ (°) | 95.980 (3), 95.419 (2), 111.960 (2) |
V (Å3) | 1718.32 (15) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.22 × 0.18 × 0.14 |
Data collection | |
Diffractometer | Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SORTAV; Blessing, 1995) |
Tmin, Tmax | 0.918, 0.989 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 10769, 6622, 4089 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.624 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.057, 0.167, 1.10 |
No. of reflections | 6622 |
No. of parameters | 448 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.33, −0.25 |
Computer programs: COLLECT (Nonius, 2002), DENZO-SMN (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), SHELXTL (Sheldrick, 2008), PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1OA···O3Ai | 0.96 (4) | 1.75 (4) | 2.689 (3) | 165 (3) |
O1B—H1OB···O3Bii | 0.88 (3) | 1.84 (4) | 2.714 (3) | 179 (4) |
Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) −x+1, −y+1, −z. |
Acknowledgements
The authors wish to acknowledge NSERC Canada and the University of Toronto for funding.
References
Altomare, A., Cascarano, G., Giacovazzo, C., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Bernstein, J., Davis, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Blessing, R. H. (1995). Acta Cryst. A51, 33–38. CrossRef CAS Web of Science IUCr Journals Google Scholar
Nonius (2002). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
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. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. 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.
We have recently studied the addition of aryl groups to a 3-aza-2-oxabicyclo[2.2.1]hept-5-ene system using a [Rh(COD)Cl]2 (COD = cyclooctadiene) catalyst. The reaction produces two stereoisomers, the absolute stereochemistry of the title major isomer,(I), was determined by single-crystal X-ray diffraction.
The asymmetric unit of (I) contains two independent molecules [A and B] which are shown in Figs 1 and 2. In the crystal structure, each type of molecule is linked into a centrosymmetric dimer via intermolecular O—H···O hydrogen bonds (Fig. 3). Each dimer forms a R22(10) graph set (Bernstein et al., 1995).