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The identity of the major product of Ru-catalysed alkene metathesis of two polyene substrates has been determined using density functional theory (DFT) NMR prediction, a 1H–1H Total Correlated Spectroscopy (TOCSY) NMR experiment and ultimately by single-crystal X-ray crystallography. The substrates were designed as those that would potentially allow expedient access to the trans-decalin skeleton of the natural product (−)-euonyminol, but the product was found to be a bis-cyclopentenyl-β-cyanohydrin [1-(1-hydroxycyclopent-3-en-1-yl)cyclopent-3-ene-1-carbonitrile, C11H13NO] rather than the trans-2,3,6,7-dehydrodecalin-β-cyanohydrin.
Supporting information
Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al.,
2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and Mercury (Macrae et al.,
2008).
1-(1-Hydroxycyclopent-3-en-1-yl)cyclopent-3-ene-1-carbonitrile
top
Crystal data top
C11H13NO | F(000) = 752 |
Mr = 175.22 | Dx = 1.242 Mg m−3 |
Monoclinic, P21/n | Cu Kα radiation, λ = 1.54178 Å |
a = 6.2966 (6) Å | Cell parameters from 3592 reflections |
b = 25.416 (4) Å | θ = 3.8–78.0° |
c = 11.7111 (13) Å | µ = 0.63 mm−1 |
β = 90.162 (8)° | T = 100 K |
V = 1874.2 (4) Å3 | Needle, colourless |
Z = 8 | 0.50 × 0.06 × 0.06 mm |
Data collection top
Agilent SuperNova (Dual, Cu at zero, Atlas) diffractometer | 3793 independent reflections |
Radiation source: SuperNova (Cu) X-ray Source | 3151 reflections with I > 2σ(I) |
Mirror monochromator | Rint = 0.032 |
Detector resolution: 10.5598 pixels mm-1 | θmax = 74.4°, θmin = 9.2° |
ω scans | h = −7→6 |
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011) | k = −31→29 |
Tmin = 0.822, Tmax = 1.000 | l = −14→14 |
8275 measured reflections | |
Refinement top
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)] = 0.045 | H atoms treated by a mixture of independent and constrained refinement |
wR(F2) = 0.141 | w = 1/[σ2(Fo2) + (0.0775P)2 + 0.5P] where P = (Fo2 + 2Fc2)/3 |
S = 1.01 | (Δ/σ)max < 0.001 |
3793 reflections | Δρmax = 0.30 e Å−3 |
281 parameters | Δρmin = −0.21 e Å−3 |
0 restraints | Extinction correction: SHELXTL (Sheldrick, 2001), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.0013 (4) |
Special details top
Experimental. CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm. |
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | Occ. (<1) |
O1A | 0.76628 (16) | 0.44288 (4) | 0.15537 (9) | 0.0276 (2) | |
H1A | 0.677 (4) | 0.4435 (10) | 0.096 (2) | 0.056 (7)* | |
N1A | 0.4874 (2) | 0.55946 (5) | 0.04558 (11) | 0.0297 (3) | |
C1A | 0.7478 (2) | 0.53532 (5) | 0.21184 (12) | 0.0238 (3) | |
C2A | 0.9832 (2) | 0.54423 (6) | 0.17483 (13) | 0.0284 (3) | |
H2AA | 1.0611 | 0.5105 | 0.1703 | 0.034* | |
H2AB | 0.9906 | 0.5621 | 0.0998 | 0.034* | |
C3A | 1.0710 (2) | 0.57836 (6) | 0.26749 (15) | 0.0339 (4) | |
H3AA | 1.2164 | 0.5881 | 0.2725 | 0.041* | |
C4A | 0.9268 (2) | 0.59361 (6) | 0.34137 (14) | 0.0328 (3) | |
H4AA | 0.9573 | 0.6151 | 0.4058 | 0.039* | |
C5A | 0.7094 (2) | 0.57357 (6) | 0.31326 (12) | 0.0279 (3) | |
H5AA | 0.6140 | 0.6027 | 0.2906 | 0.034* | |
H5AB | 0.6467 | 0.5549 | 0.3792 | 0.034* | |
C6A | 0.7035 (2) | 0.47709 (5) | 0.24580 (11) | 0.0241 (3) | |
C7A | 0.8317 (2) | 0.45963 (6) | 0.35194 (13) | 0.0295 (3) | |
H7AA | 0.9509 | 0.4363 | 0.3301 | 0.035* | |
H7AB | 0.8888 | 0.4904 | 0.3937 | 0.035* | |
C8A | 0.6719 (3) | 0.43061 (6) | 0.42280 (13) | 0.0326 (3) | |
H8AA | 0.7068 | 0.4114 | 0.4898 | 0.039* | |
C9A | 0.4767 (3) | 0.43481 (6) | 0.38147 (13) | 0.0310 (3) | |
H9AA | 0.3559 | 0.4188 | 0.4153 | 0.037* | |
C10A | 0.4676 (2) | 0.46748 (6) | 0.27596 (12) | 0.0267 (3) | |
H10A | 0.3932 | 0.5011 | 0.2903 | 0.032* | |
H10B | 0.3938 | 0.4485 | 0.2136 | 0.032* | |
C11A | 0.6035 (2) | 0.54883 (5) | 0.11749 (12) | 0.0234 (3) | |
O1B | 1.1375 (3) | 0.38377 (8) | 0.1252 (4) | 0.0291 (6) | 0.617 (7) |
H1B | 1.014 (5) | 0.3970 (11) | 0.142 (3) | 0.073 (8)* | 0.617 (7) |
N1B | 1.0975 (2) | 0.19591 (5) | 0.14071 (13) | 0.0390 (3) | 0.617 (7) |
C1B | 1.0986 (4) | 0.29643 (17) | 0.2025 (2) | 0.0267 (7) | 0.617 (7) |
C2B | 0.8870 (2) | 0.31141 (7) | 0.26723 (14) | 0.0337 (4) | 0.617 (7) |
H2BA | 0.8329 | 0.3460 | 0.2416 | 0.040* | 0.617 (7) |
H2BB | 0.7757 | 0.2845 | 0.2545 | 0.040* | 0.617 (7) |
C3B | 0.9526 (3) | 0.31317 (7) | 0.39052 (15) | 0.0387 (4) | 0.617 (7) |
H3BA | 0.8553 | 0.3153 | 0.4522 | 0.046* | 0.617 (7) |
C4B | 1.1596 (3) | 0.31135 (7) | 0.40352 (14) | 0.0393 (4) | 0.617 (7) |
H4BA | 1.2286 | 0.3120 | 0.4758 | 0.047* | 0.617 (7) |
C5B | 1.2751 (2) | 0.30814 (6) | 0.29232 (14) | 0.0335 (3) | 0.617 (7) |
H5BA | 1.3819 | 0.2796 | 0.2939 | 0.040* | 0.617 (7) |
H5BB | 1.3475 | 0.3418 | 0.2751 | 0.040* | 0.617 (7) |
C6B | 1.1280 (4) | 0.32994 (14) | 0.0936 (2) | 0.0271 (8) | 0.617 (7) |
C7B | 1.3381 (3) | 0.31425 (8) | 0.03349 (16) | 0.0428 (4) | 0.617 (7) |
H7BA | 1.4523 | 0.3399 | 0.0506 | 0.051* | 0.617 (7) |
H7BB | 1.3850 | 0.2788 | 0.0576 | 0.051* | 0.617 (7) |
C8B | 1.2818 (4) | 0.31502 (8) | −0.09020 (17) | 0.0506 (5) | 0.617 (7) |
H8BA | 1.3833 | 0.3147 | −0.1501 | 0.061* | 0.617 (7) |
C9B | 1.0756 (4) | 0.31619 (7) | −0.10667 (15) | 0.0512 (5) | 0.617 (7) |
H9BA | 1.0115 | 0.3166 | −0.1802 | 0.061* | 0.617 (7) |
C10B | 0.9514 (3) | 0.31683 (7) | 0.00239 (15) | 0.0406 (4) | 0.617 (7) |
H10C | 0.8852 | 0.2822 | 0.0175 | 0.049* | 0.617 (7) |
H10D | 0.8398 | 0.3442 | 0.0008 | 0.049* | 0.617 (7) |
C11B | 1.1002 (4) | 0.24021 (12) | 0.1708 (4) | 0.0286 (7) | 0.617 (7) |
O1C | 1.1255 (5) | 0.38036 (13) | 0.1839 (6) | 0.0287 (9) | 0.383 (7) |
H1C | 1.014 (5) | 0.3970 (11) | 0.142 (3) | 0.073 (8)* | 0.383 (7) |
N1C | 1.0975 (2) | 0.19591 (5) | 0.14071 (13) | 0.0390 (3) | 0.383 (7) |
C1C | 1.0978 (6) | 0.3259 (3) | 0.2061 (3) | 0.0257 (11) | 0.383 (7) |
C2C | 0.8870 (2) | 0.31141 (7) | 0.26723 (14) | 0.0337 (4) | 0.383 (7) |
H2CA | 0.7739 | 0.3374 | 0.2506 | 0.040* | 0.383 (7) |
H2CB | 0.8373 | 0.2759 | 0.2450 | 0.040* | 0.383 (7) |
C3C | 0.9526 (3) | 0.31317 (7) | 0.39052 (15) | 0.0387 (4) | 0.383 (7) |
H3CA | 0.8553 | 0.3153 | 0.4522 | 0.046* | 0.383 (7) |
C4C | 1.1596 (3) | 0.31135 (7) | 0.40352 (14) | 0.0393 (4) | 0.383 (7) |
H4CA | 1.2286 | 0.3120 | 0.4758 | 0.047* | 0.383 (7) |
C5C | 1.2751 (2) | 0.30814 (6) | 0.29232 (14) | 0.0335 (3) | 0.383 (7) |
H5CA | 1.3236 | 0.2718 | 0.2764 | 0.040* | 0.383 (7) |
H5CB | 1.3985 | 0.3322 | 0.2907 | 0.040* | 0.383 (7) |
C6C | 1.1177 (6) | 0.2962 (2) | 0.0917 (3) | 0.0262 (13) | 0.383 (7) |
C7C | 1.3381 (3) | 0.31425 (8) | 0.03349 (16) | 0.0428 (4) | 0.383 (7) |
H7CA | 1.3822 | 0.3495 | 0.0604 | 0.051* | 0.383 (7) |
H7CB | 1.4532 | 0.2887 | 0.0494 | 0.051* | 0.383 (7) |
C8C | 1.2818 (4) | 0.31502 (8) | −0.09020 (17) | 0.0506 (5) | 0.383 (7) |
H8CA | 1.3833 | 0.3147 | −0.1501 | 0.061* | 0.383 (7) |
C9C | 1.0756 (4) | 0.31619 (7) | −0.10667 (15) | 0.0512 (5) | 0.383 (7) |
H9CA | 1.0115 | 0.3166 | −0.1802 | 0.061* | 0.383 (7) |
C10C | 0.9514 (3) | 0.31683 (7) | 0.00239 (15) | 0.0406 (4) | 0.383 (7) |
H10E | 0.8265 | 0.2933 | −0.0023 | 0.049* | 0.383 (7) |
H10F | 0.9033 | 0.3528 | 0.0215 | 0.049* | 0.383 (7) |
C11C | 1.1009 (7) | 0.23852 (18) | 0.1137 (6) | 0.0282 (11) | 0.383 (7) |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
O1A | 0.0314 (5) | 0.0243 (5) | 0.0272 (5) | 0.0067 (4) | −0.0062 (4) | −0.0050 (4) |
N1A | 0.0337 (6) | 0.0250 (6) | 0.0303 (6) | 0.0025 (5) | −0.0055 (5) | −0.0023 (5) |
C1A | 0.0239 (6) | 0.0234 (7) | 0.0241 (6) | 0.0024 (5) | −0.0032 (5) | −0.0015 (5) |
C2A | 0.0235 (7) | 0.0285 (7) | 0.0332 (7) | 0.0017 (5) | −0.0002 (5) | −0.0017 (6) |
C3A | 0.0257 (7) | 0.0282 (7) | 0.0477 (9) | 0.0000 (6) | −0.0086 (6) | −0.0024 (7) |
C4A | 0.0331 (8) | 0.0283 (7) | 0.0370 (8) | 0.0027 (6) | −0.0114 (6) | −0.0078 (6) |
C5A | 0.0307 (7) | 0.0280 (7) | 0.0251 (7) | 0.0025 (5) | −0.0023 (5) | −0.0062 (5) |
C6A | 0.0261 (7) | 0.0233 (7) | 0.0231 (6) | 0.0024 (5) | −0.0032 (5) | −0.0012 (5) |
C7A | 0.0309 (7) | 0.0295 (7) | 0.0282 (7) | 0.0030 (6) | −0.0078 (6) | 0.0003 (6) |
C8A | 0.0421 (8) | 0.0312 (8) | 0.0245 (7) | 0.0040 (6) | −0.0037 (6) | 0.0015 (6) |
C9A | 0.0355 (8) | 0.0288 (7) | 0.0287 (7) | 0.0006 (6) | 0.0006 (6) | 0.0007 (6) |
C10A | 0.0259 (7) | 0.0259 (7) | 0.0283 (7) | 0.0001 (5) | −0.0043 (5) | 0.0010 (6) |
C11A | 0.0249 (6) | 0.0196 (6) | 0.0257 (6) | 0.0011 (5) | −0.0012 (5) | −0.0021 (5) |
O1B | 0.0266 (9) | 0.0182 (9) | 0.0425 (17) | 0.0001 (6) | 0.0024 (10) | −0.0024 (10) |
N1B | 0.0450 (8) | 0.0254 (7) | 0.0468 (8) | 0.0000 (5) | 0.0131 (6) | 0.0016 (6) |
C1B | 0.0273 (12) | 0.0227 (19) | 0.0303 (12) | 0.0003 (10) | 0.0030 (9) | −0.0028 (11) |
C2B | 0.0293 (7) | 0.0368 (8) | 0.0349 (8) | 0.0018 (6) | 0.0075 (6) | 0.0006 (6) |
C3B | 0.0530 (10) | 0.0313 (8) | 0.0318 (8) | 0.0028 (7) | 0.0121 (7) | 0.0004 (6) |
C4B | 0.0580 (11) | 0.0291 (8) | 0.0307 (8) | 0.0048 (7) | −0.0047 (7) | −0.0014 (6) |
C5B | 0.0320 (8) | 0.0311 (8) | 0.0374 (8) | 0.0031 (6) | −0.0044 (6) | −0.0039 (6) |
C6B | 0.0310 (12) | 0.0192 (19) | 0.0310 (12) | −0.0017 (9) | 0.0036 (9) | −0.0039 (9) |
C7B | 0.0399 (9) | 0.0454 (10) | 0.0431 (9) | 0.0014 (7) | 0.0180 (7) | −0.0001 (8) |
C8B | 0.0782 (14) | 0.0358 (9) | 0.0380 (9) | −0.0019 (9) | 0.0223 (9) | −0.0013 (8) |
C9B | 0.0953 (17) | 0.0294 (8) | 0.0289 (8) | −0.0054 (9) | −0.0014 (9) | −0.0006 (7) |
C10B | 0.0476 (9) | 0.0393 (9) | 0.0347 (8) | −0.0011 (7) | −0.0077 (7) | −0.0001 (7) |
C11B | 0.0276 (12) | 0.0260 (14) | 0.0323 (18) | −0.0012 (9) | 0.0043 (12) | 0.0031 (13) |
O1C | 0.0264 (15) | 0.0183 (14) | 0.041 (3) | −0.0011 (10) | 0.0009 (15) | −0.0021 (16) |
N1C | 0.0450 (8) | 0.0254 (7) | 0.0468 (8) | 0.0000 (5) | 0.0131 (6) | 0.0016 (6) |
C1C | 0.0259 (18) | 0.022 (3) | 0.029 (2) | 0.0023 (16) | 0.0009 (13) | −0.0029 (17) |
C2C | 0.0293 (7) | 0.0368 (8) | 0.0349 (8) | 0.0018 (6) | 0.0075 (6) | 0.0006 (6) |
C3C | 0.0530 (10) | 0.0313 (8) | 0.0318 (8) | 0.0028 (7) | 0.0121 (7) | 0.0004 (6) |
C4C | 0.0580 (11) | 0.0291 (8) | 0.0307 (8) | 0.0048 (7) | −0.0047 (7) | −0.0014 (6) |
C5C | 0.0320 (8) | 0.0311 (8) | 0.0374 (8) | 0.0031 (6) | −0.0044 (6) | −0.0039 (6) |
C6C | 0.0272 (19) | 0.022 (3) | 0.0299 (19) | −0.0032 (14) | 0.0056 (14) | −0.0006 (15) |
C7C | 0.0399 (9) | 0.0454 (10) | 0.0431 (9) | 0.0014 (7) | 0.0180 (7) | −0.0001 (8) |
C8C | 0.0782 (14) | 0.0358 (9) | 0.0380 (9) | −0.0019 (9) | 0.0223 (9) | −0.0013 (8) |
C9C | 0.0953 (17) | 0.0294 (8) | 0.0289 (8) | −0.0054 (9) | −0.0014 (9) | −0.0006 (7) |
C10C | 0.0476 (9) | 0.0393 (9) | 0.0347 (8) | −0.0011 (7) | −0.0077 (7) | −0.0001 (7) |
C11C | 0.030 (2) | 0.023 (2) | 0.032 (3) | 0.0017 (14) | 0.004 (2) | −0.004 (2) |
Geometric parameters (Å, º) top
O1A—C6A | 1.4270 (17) | N1B—C11B | 1.180 (4) |
O1A—H1A | 0.90 (3) | C1B—C11B | 1.476 (6) |
N1A—C11A | 1.146 (2) | C1B—C6B | 1.545 (5) |
C1A—C11A | 1.4693 (18) | C1B—C5B | 1.556 (3) |
C1A—C5A | 1.5543 (19) | C1B—C2B | 1.581 (3) |
C1A—C6A | 1.5579 (19) | C2B—C3B | 1.501 (2) |
C1A—C2A | 1.5624 (19) | C2B—H2BA | 0.9900 |
C2A—C3A | 1.494 (2) | C2B—H2BB | 0.9900 |
C2A—H2AA | 0.9900 | C3B—C4B | 1.313 (3) |
C2A—H2AB | 0.9900 | C3B—H3BA | 0.9500 |
C3A—C4A | 1.314 (2) | C4B—C5B | 1.495 (2) |
C3A—H3AA | 0.9500 | C4B—H4BA | 0.9500 |
C4A—C5A | 1.496 (2) | C5B—H5BA | 0.9900 |
C4A—H4AA | 0.9500 | C5B—H5BB | 0.9900 |
C5A—H5AA | 0.9900 | C6B—C7B | 1.552 (3) |
C5A—H5AB | 0.9900 | C6B—C10B | 1.575 (3) |
C6A—C7A | 1.5453 (18) | C7B—C8B | 1.490 (3) |
C6A—C10A | 1.5472 (19) | C7B—H7BA | 0.9900 |
C7A—C8A | 1.500 (2) | C7B—H7BB | 0.9900 |
C7A—H7AA | 0.9900 | C8B—C9B | 1.313 (3) |
C7A—H7AB | 0.9900 | C8B—H8BA | 0.9500 |
C8A—C9A | 1.324 (2) | C9B—C10B | 1.499 (3) |
C8A—H8AA | 0.9500 | C9B—H9BA | 0.9500 |
C9A—C10A | 1.490 (2) | C10B—H10C | 0.9900 |
C9A—H9AA | 0.9500 | C10B—H10D | 0.9900 |
C10A—H10A | 0.9900 | O1C—C1C | 1.418 (9) |
C10A—H10B | 0.9900 | O1C—H1B | 0.95 (3) |
O1B—C6B | 1.419 (4) | O1C—H1C | 0.95 (3) |
O1B—H1B | 0.87 (3) | C1C—C6C | 1.543 (7) |
O1B—H1C | 0.87 (3) | C6C—C11C | 1.492 (7) |
| | | |
C6A—O1A—H1A | 113.3 (16) | C11B—C1B—C5B | 110.5 (2) |
C11A—C1A—C5A | 109.36 (11) | C6B—C1B—C5B | 111.4 (3) |
C11A—C1A—C6A | 107.66 (11) | C11B—C1B—C2B | 111.1 (2) |
C5A—C1A—C6A | 111.77 (12) | C6B—C1B—C2B | 111.5 (3) |
C11A—C1A—C2A | 110.05 (12) | C5B—C1B—C2B | 103.36 (19) |
C5A—C1A—C2A | 105.72 (11) | C3B—C2B—C1B | 103.77 (15) |
C6A—C1A—C2A | 112.28 (11) | C3B—C2B—H2BA | 111.0 |
C3A—C2A—C1A | 103.41 (12) | C1B—C2B—H2BA | 111.0 |
C3A—C2A—H2AA | 111.1 | C3B—C2B—H2BB | 111.0 |
C1A—C2A—H2AA | 111.1 | C1B—C2B—H2BB | 111.0 |
C3A—C2A—H2AB | 111.1 | H2BA—C2B—H2BB | 109.0 |
C1A—C2A—H2AB | 111.1 | C4B—C3B—C2B | 112.39 (15) |
H2AA—C2A—H2AB | 109.0 | C4B—C3B—H3BA | 123.8 |
C4A—C3A—C2A | 113.25 (14) | C2B—C3B—H3BA | 123.8 |
C4A—C3A—H3AA | 123.4 | C3B—C4B—C5B | 112.70 (15) |
C2A—C3A—H3AA | 123.4 | C3B—C4B—H4BA | 123.7 |
C3A—C4A—C5A | 112.82 (13) | C5B—C4B—H4BA | 123.7 |
C3A—C4A—H4AA | 123.6 | C4B—C5B—C1B | 104.53 (15) |
C5A—C4A—H4AA | 123.6 | C4B—C5B—H5BA | 110.8 |
C4A—C5A—C1A | 103.72 (12) | C1B—C5B—H5BA | 110.8 |
C4A—C5A—H5AA | 111.0 | C4B—C5B—H5BB | 110.8 |
C1A—C5A—H5AA | 111.0 | C1B—C5B—H5BB | 110.8 |
C4A—C5A—H5AB | 111.0 | H5BA—C5B—H5BB | 108.9 |
C1A—C5A—H5AB | 111.0 | O1B—C6B—C1B | 108.7 (3) |
H5AA—C5A—H5AB | 109.0 | O1B—C6B—C7B | 109.3 (2) |
O1A—C6A—C7A | 106.07 (11) | C1B—C6B—C7B | 109.7 (2) |
O1A—C6A—C10A | 109.96 (11) | O1B—C6B—C10B | 114.2 (2) |
C7A—C6A—C10A | 105.71 (11) | C1B—C6B—C10B | 110.9 (2) |
O1A—C6A—C1A | 109.83 (11) | C7B—C6B—C10B | 103.82 (18) |
C7A—C6A—C1A | 112.63 (11) | C8B—C7B—C6B | 103.69 (17) |
C10A—C6A—C1A | 112.38 (11) | C8B—C7B—H7BA | 111.0 |
C8A—C7A—C6A | 103.67 (12) | C6B—C7B—H7BA | 111.0 |
C8A—C7A—H7AA | 111.0 | C8B—C7B—H7BB | 111.0 |
C6A—C7A—H7AA | 111.0 | C6B—C7B—H7BB | 111.0 |
C8A—C7A—H7AB | 111.0 | H7BA—C7B—H7BB | 109.0 |
C6A—C7A—H7AB | 111.0 | C9B—C8B—C7B | 112.06 (16) |
H7AA—C7A—H7AB | 109.0 | C9B—C8B—H8BA | 124.0 |
C9A—C8A—C7A | 112.44 (14) | C7B—C8B—H8BA | 124.0 |
C9A—C8A—H8AA | 123.8 | C8B—C9B—C10B | 113.14 (17) |
C7A—C8A—H8AA | 123.8 | C8B—C9B—H9BA | 123.4 |
C8A—C9A—C10A | 112.44 (14) | C10B—C9B—H9BA | 123.4 |
C8A—C9A—H9AA | 123.8 | C9B—C10B—C6B | 102.19 (16) |
C10A—C9A—H9AA | 123.8 | C9B—C10B—H10C | 111.3 |
C9A—C10A—C6A | 104.05 (11) | C6B—C10B—H10C | 111.3 |
C9A—C10A—H10A | 110.9 | C9B—C10B—H10D | 111.3 |
C6A—C10A—H10A | 110.9 | C6B—C10B—H10D | 111.3 |
C9A—C10A—H10B | 110.9 | H10C—C10B—H10D | 109.2 |
C6A—C10A—H10B | 110.9 | N1B—C11B—C1B | 176.9 (4) |
H10A—C10A—H10B | 109.0 | C1C—O1C—H1B | 115.9 (18) |
N1A—C11A—C1A | 178.51 (15) | C1C—O1C—H1C | 115.9 (18) |
C6B—O1B—H1B | 113.3 (19) | O1C—C1C—C6C | 108.0 (5) |
C6B—O1B—H1C | 113.3 (19) | C11C—C6C—C1C | 109.0 (5) |
C11B—C1B—C6B | 108.9 (3) | | |
| | | |
C11A—C1A—C2A—C3A | 127.62 (13) | C6B—C1B—C2B—C3B | −136.6 (2) |
C5A—C1A—C2A—C3A | 9.63 (15) | C5B—C1B—C2B—C3B | −16.8 (3) |
C6A—C1A—C2A—C3A | −112.49 (13) | C1B—C2B—C3B—C4B | 11.1 (2) |
C1A—C2A—C3A—C4A | −5.79 (18) | C2B—C3B—C4B—C5B | 0.1 (2) |
C2A—C3A—C4A—C5A | −0.8 (2) | C3B—C4B—C5B—C1B | −11.5 (2) |
C3A—C4A—C5A—C1A | 7.08 (18) | C11B—C1B—C5B—C4B | −102.0 (2) |
C11A—C1A—C5A—C4A | −128.51 (13) | C6B—C1B—C5B—C4B | 136.8 (2) |
C6A—C1A—C5A—C4A | 112.38 (13) | C2B—C1B—C5B—C4B | 17.0 (3) |
C2A—C1A—C5A—C4A | −10.06 (15) | C11B—C1B—C6B—O1B | −177.0 (2) |
C11A—C1A—C6A—O1A | 67.25 (14) | C5B—C1B—C6B—O1B | −54.9 (3) |
C5A—C1A—C6A—O1A | −172.64 (11) | C2B—C1B—C6B—O1B | 60.0 (3) |
C2A—C1A—C6A—O1A | −54.03 (14) | C11B—C1B—C6B—C7B | −57.5 (3) |
C11A—C1A—C6A—C7A | −174.77 (11) | C5B—C1B—C6B—C7B | 64.6 (4) |
C5A—C1A—C6A—C7A | −54.66 (15) | C2B—C1B—C6B—C7B | 179.54 (19) |
C2A—C1A—C6A—C7A | 63.95 (15) | C11B—C1B—C6B—C10B | 56.6 (3) |
C11A—C1A—C6A—C10A | −55.50 (15) | C5B—C1B—C6B—C10B | 178.76 (19) |
C5A—C1A—C6A—C10A | 64.61 (14) | C2B—C1B—C6B—C10B | −66.3 (4) |
C2A—C1A—C6A—C10A | −176.78 (11) | O1B—C6B—C7B—C8B | −100.8 (2) |
O1A—C6A—C7A—C8A | −104.46 (13) | C1B—C6B—C7B—C8B | 140.0 (2) |
C10A—C6A—C7A—C8A | 12.29 (15) | C10B—C6B—C7B—C8B | 21.4 (3) |
C1A—C6A—C7A—C8A | 135.37 (12) | C6B—C7B—C8B—C9B | −14.4 (3) |
C6A—C7A—C8A—C9A | −7.82 (18) | C7B—C8B—C9B—C10B | 0.4 (2) |
C7A—C8A—C9A—C10A | −0.30 (19) | C8B—C9B—C10B—C6B | 13.5 (2) |
C8A—C9A—C10A—C6A | 8.30 (17) | O1B—C6B—C10B—C9B | 98.0 (2) |
O1A—C6A—C10A—C9A | 101.58 (13) | C1B—C6B—C10B—C9B | −138.7 (2) |
C7A—C6A—C10A—C9A | −12.50 (14) | C7B—C6B—C10B—C9B | −20.9 (2) |
C1A—C6A—C10A—C9A | −135.74 (12) | O1C—C1C—C6C—C11C | 176.9 (3) |
C11B—C1B—C2B—C3B | 101.6 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
O1A—H1A···N1Ai | 0.90 (3) | 1.95 (3) | 2.8410 (16) | 173 (2) |
O1B—H1B···O1A | 0.87 (3) | 1.95 (3) | 2.802 (2) | 164 (3) |
O1C—H1C···O1A | 0.95 (3) | 1.95 (3) | 2.783 (3) | 144 (3) |
Symmetry code: (i) −x+1, −y+1, −z. |
Parameters for comparison of experimental 1H and 13C NMR data
for compounds (9) and (10), with predicted data at the
DFT-B3LYP/6-31G(**) level using the GIAO method (p.p.m.) top | 1H NMR | | 13C NMR | |
| cis-Decalin, (9) | Bis-cyclopentene, (10) | cis-Decalin, (9) | Bis-cyclopentene, (10) |
ATE | 1.57 | 0.81 | 50.73 | 20.23 |
MAE | 0.26 | 0.13 | 7.25 | 2.89 |
SD | 0.24 | 0.11 | 1.83 | 3.28 |
RMS | 0.29 | 0.17 | 7.47 | 3.31 |
Max | 0.43 | 0.00 | 10.94 | 6.64 |
Min | -0.15 | -0.25 | 5.10 | -3.22 |
Range | 0.59 | 0.26 | 5.83 | 9.86 |
LCE | 0.9965 | 0.9970 | 0.9979 | 0.9976 |
CMAE | 0.16 | 0.09 | 1.26 | 1.62 |
DP4 | 0.46 | 0.54 | 0.62 | 0.38 |
Baye's CMAE | 0.36 | 0.64 | 0.56 | 0.44 |
Notes: ATE = absolute total error, MAE = mean absolute error, SD = standard
deviation, RMS = root-mean-square error, Max/Min = the largest and smallest
errors, Range = Max - Min (all in p.p.m.). LCE = linear correlation
coefficient, CMAE = corrected mean absolute error, DP4 = Goodman and Smith's
DP4 probability parameter (Smith & Goodman, 2010), and Bayes' CMAE =
Bayes'
theorem probability of the two CMAE values {e.g. 1-[A/(A+B)]}. All
values are in p.p.m. with the exception of LCE (unitless) and the
probabilities; DP4 and Bayes' theorem values (unitless fraction out of 1). |
Bond lengths of the C—O and C—C(N) bonds vicinal to the central
C—C bond in bis-cyclopentenyl-β-cyanohydrin 10; evidence for a
σCO → σ*CC(N) anomeric effect in the anti conformers. topConformer | Bond lengths (Å) | |
| C—O | C—C(N) |
gauche | 1.427 (2) | 1.469 (2) |
anti (1) | 1.419 (4) | 1.476 (6) |
anti (2) | 1.418 (9) | 1.492 (7) |
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