Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803005531/ww6064sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536803005531/ww6064Isup2.hkl |
CCDC reference: 209961
The title compound, (I), was prepared according to the following procedures under a nitrogen atmosphere unless otherwise stated. To a magnetically stirred solution of 2.26 ml (4.5 mmol) of LDA (2.0 M solution in THF) was added a solution of 3-bromo-2,6-dimethoxypyridine (0.988 g, 4.5 mmol) in dried THF (5 ml) at 195 K over a period of 15 min. The reaction mixture was stirred for another 15 min and to the resulting red–brown suspension was added a solution of dicyclohexylphosphine chloride in 10 ml dried THF. The reaction was allowed to stir and reach ambient temperature overnight. 25 ml water was added to the reaction mixture and the solvent was removed under reduced pressure. The organic product was extracted with dichloromethane. The combined extract was dried with anhydrous sodium sulfate and was concentrated in vacuo to give a crude product. To the crude product in acetone solution (20 ml), 35% hydrogen peroxide (10 ml) was added slowly and the reaction was monitored by thin-layer chromatography. The product was extracted with dichloromethane. The crude product was purified by column chromatography (silica gel, hexane–ethyl acetate 6:1) to give the pure product (I) (50% yield). The crystal used for the data collection was obtained by slow evaporation from a hexane–dichloromethane (1:1) saturated solution at room temperature. Found: C 52.63, H 6.90, N 2.96%; calculated for C19H29BrNO3P: C 53.03, H 7.53, N 3.25%.
The C-bound H atoms were placed in geometrically calculated positions and included in the final refinement in the riding-model approximation.
Data collection: SMART (Siemens, 1995); cell refinement: SMART; data reduction: SHELXTL-NT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT; software used to prepare material for publication: SHELXTL-NT.
Fig. 1. The olecular structure of (I), showing ellipsoids at the 30% probability level (Siemens, 1995). |
C19H29BrNO3P | F(000) = 1792 |
Mr = 430.31 | Dx = 1.394 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 8624 reflections |
a = 9.2025 (12) Å | θ = 1–27.5° |
b = 18.759 (2) Å | µ = 2.10 mm−1 |
c = 23.761 (3) Å | T = 294 K |
β = 92.009 (3)° | Prism, colorless |
V = 4099.3 (9) Å3 | 0.30 × 0.26 × 0.24 mm |
Z = 8 |
Siemens SMART CCD area-detector diffractometer | 9427 independent reflections |
Radiation source: fine-focus sealed tube | 3936 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
ϕ and ω scans | θmax = 27.5°, θmin = 2.2° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −11→11 |
Tmin = 0.571, Tmax = 0.633 | k = −19→24 |
27403 measured reflections | l = −30→27 |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.03 | w = 1/[σ2(Fo2) + (0.035P)2] where P = (Fo2 + 2Fc2)/3 |
9427 reflections | (Δ/σ)max = 0.002 |
451 parameters | Δρmax = 0.91 e Å−3 |
0 restraints | Δρmin = −0.60 e Å−3 |
C19H29BrNO3P | V = 4099.3 (9) Å3 |
Mr = 430.31 | Z = 8 |
Monoclinic, P21/n | Mo Kα radiation |
a = 9.2025 (12) Å | µ = 2.10 mm−1 |
b = 18.759 (2) Å | T = 294 K |
c = 23.761 (3) Å | 0.30 × 0.26 × 0.24 mm |
β = 92.009 (3)° |
Siemens SMART CCD area-detector diffractometer | 9427 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 3936 reflections with I > 2σ(I) |
Tmin = 0.571, Tmax = 0.633 | Rint = 0.061 |
27403 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 0 restraints |
wR(F2) = 0.117 | H-atom parameters constrained |
S = 1.03 | Δρmax = 0.91 e Å−3 |
9427 reflections | Δρmin = −0.60 e Å−3 |
451 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 | ||
Br1 | 0.37202 (5) | 0.30717 (3) | 0.55442 (2) | 0.06490 (18) | |
P1 | 0.22148 (13) | 0.35103 (7) | 0.41928 (5) | 0.0532 (3) | |
O1 | 0.1201 (3) | 0.36109 (17) | 0.37024 (11) | 0.0722 (10) | |
O2 | 0.1533 (3) | 0.22404 (17) | 0.61400 (13) | 0.0655 (9) | |
O3 | −0.2073 (4) | 0.20364 (19) | 0.47620 (12) | 0.0770 (10) | |
N1 | −0.0290 (4) | 0.21495 (19) | 0.54593 (14) | 0.0493 (10) | |
C1 | 0.3831 (5) | 0.2989 (2) | 0.40401 (18) | 0.0543 (12) | |
H1A | 0.4315 | 0.2889 | 0.4405 | 0.065* | |
C2 | 0.4918 (6) | 0.3365 (3) | 0.3703 (2) | 0.0870 (18) | |
H2A | 0.5296 | 0.3769 | 0.3918 | 0.104* | |
H2B | 0.4439 | 0.3550 | 0.3364 | 0.104* | |
C3 | 0.6155 (6) | 0.2907 (3) | 0.3543 (3) | 0.0944 (19) | |
H3A | 0.6778 | 0.2825 | 0.3875 | 0.113* | |
H3B | 0.6722 | 0.3163 | 0.3272 | 0.113* | |
C4 | 0.5727 (7) | 0.2203 (3) | 0.3297 (3) | 0.107 (2) | |
H4A | 0.5306 | 0.2275 | 0.2921 | 0.128* | |
H4B | 0.6587 | 0.1909 | 0.3266 | 0.128* | |
C5 | 0.4682 (7) | 0.1835 (3) | 0.3639 (3) | 0.118 (2) | |
H5A | 0.5180 | 0.1668 | 0.3981 | 0.142* | |
H5B | 0.4327 | 0.1419 | 0.3434 | 0.142* | |
C6 | 0.3402 (6) | 0.2279 (3) | 0.3798 (2) | 0.0917 (19) | |
H6A | 0.2774 | 0.2353 | 0.3467 | 0.110* | |
H6B | 0.2850 | 0.2021 | 0.4073 | 0.110* | |
C7 | 0.2827 (5) | 0.4360 (2) | 0.44960 (16) | 0.0450 (11) | |
H7A | 0.3785 | 0.4286 | 0.4680 | 0.054* | |
C8 | 0.1816 (5) | 0.4673 (3) | 0.49314 (19) | 0.0656 (14) | |
H8A | 0.0846 | 0.4720 | 0.4763 | 0.079* | |
H8B | 0.1765 | 0.4348 | 0.5247 | 0.079* | |
C9 | 0.2329 (5) | 0.5393 (3) | 0.51426 (19) | 0.0683 (14) | |
H9A | 0.1632 | 0.5581 | 0.5401 | 0.082* | |
H9B | 0.3252 | 0.5338 | 0.5348 | 0.082* | |
C10 | 0.2508 (6) | 0.5915 (3) | 0.4669 (2) | 0.0839 (17) | |
H10A | 0.2910 | 0.6357 | 0.4818 | 0.101* | |
H10B | 0.1565 | 0.6018 | 0.4492 | 0.101* | |
C11 | 0.3509 (6) | 0.5613 (3) | 0.4233 (2) | 0.0799 (17) | |
H11A | 0.3556 | 0.5944 | 0.3920 | 0.096* | |
H11B | 0.4482 | 0.5566 | 0.4400 | 0.096* | |
C12 | 0.3001 (5) | 0.4890 (2) | 0.40137 (18) | 0.0641 (14) | |
H12A | 0.3701 | 0.4706 | 0.3755 | 0.077* | |
H12B | 0.2078 | 0.4945 | 0.3809 | 0.077* | |
C13 | 0.1291 (5) | 0.2984 (2) | 0.47399 (16) | 0.0440 (11) | |
C14 | 0.1844 (4) | 0.2811 (2) | 0.52684 (18) | 0.0479 (12) | |
C15 | 0.1003 (5) | 0.2396 (2) | 0.56209 (18) | 0.0498 (12) | |
C16 | −0.0792 (5) | 0.2307 (3) | 0.4938 (2) | 0.0539 (12) | |
C17 | −0.0032 (5) | 0.2738 (2) | 0.45722 (19) | 0.0572 (13) | |
H17A | −0.0430 | 0.2855 | 0.4219 | 0.069* | |
C18 | 0.0722 (5) | 0.1757 (3) | 0.64868 (19) | 0.0787 (17) | |
H18A | 0.1228 | 0.1696 | 0.6844 | 0.118* | |
H18B | 0.0627 | 0.1304 | 0.6301 | 0.118* | |
H18C | −0.0227 | 0.1951 | 0.6545 | 0.118* | |
C19 | −0.2789 (6) | 0.1560 (3) | 0.5116 (2) | 0.101 (2) | |
H19A | −0.3690 | 0.1412 | 0.4936 | 0.151* | |
H19B | −0.2981 | 0.1792 | 0.5466 | 0.151* | |
H19C | −0.2185 | 0.1150 | 0.5187 | 0.151* | |
Br2 | 0.85647 (5) | 0.04305 (3) | 0.747128 (18) | 0.06861 (19) | |
P2 | 0.49520 (12) | 0.07662 (7) | 0.69441 (4) | 0.0456 (3) | |
O4 | 0.3660 (3) | 0.08126 (16) | 0.65554 (11) | 0.0575 (8) | |
O5 | 1.0107 (3) | −0.03275 (18) | 0.65904 (12) | 0.0719 (10) | |
O6 | 0.6551 (4) | −0.04846 (18) | 0.51877 (12) | 0.0789 (11) | |
N2 | 0.8342 (4) | −0.04124 (19) | 0.58850 (15) | 0.0533 (10) | |
C20 | 0.4615 (5) | 0.0253 (2) | 0.75805 (16) | 0.0527 (12) | |
H20A | 0.5261 | 0.0436 | 0.7884 | 0.063* | |
C21 | 0.4891 (6) | −0.0536 (2) | 0.75249 (19) | 0.0708 (15) | |
H21A | 0.5902 | −0.0611 | 0.7439 | 0.085* | |
H21B | 0.4296 | −0.0722 | 0.7213 | 0.085* | |
C22 | 0.4556 (7) | −0.0946 (3) | 0.8055 (2) | 0.0893 (18) | |
H22A | 0.5215 | −0.0796 | 0.8359 | 0.107* | |
H22B | 0.4708 | −0.1451 | 0.7992 | 0.107* | |
C23 | 0.3000 (7) | −0.0823 (3) | 0.8222 (2) | 0.104 (2) | |
H23A | 0.2337 | −0.1029 | 0.7939 | 0.125* | |
H23B | 0.2837 | −0.1057 | 0.8578 | 0.125* | |
C24 | 0.2700 (7) | −0.0042 (4) | 0.8275 (2) | 0.116 (2) | |
H24A | 0.3274 | 0.0146 | 0.8592 | 0.139* | |
H24B | 0.1682 | 0.0025 | 0.8354 | 0.139* | |
C25 | 0.3048 (6) | 0.0376 (3) | 0.7749 (2) | 0.0874 (18) | |
H25A | 0.2899 | 0.0880 | 0.7817 | 0.105* | |
H25B | 0.2390 | 0.0232 | 0.7442 | 0.105* | |
C26 | 0.5657 (4) | 0.1628 (2) | 0.71600 (16) | 0.0457 (11) | |
H26A | 0.6390 | 0.1547 | 0.7462 | 0.055* | |
C27 | 0.4483 (5) | 0.2098 (2) | 0.73966 (19) | 0.0647 (14) | |
H27A | 0.4069 | 0.1862 | 0.7717 | 0.078* | |
H27B | 0.3712 | 0.2164 | 0.7112 | 0.078* | |
C28 | 0.5077 (6) | 0.2828 (3) | 0.7581 (2) | 0.0740 (16) | |
H28A | 0.4287 | 0.3121 | 0.7710 | 0.089* | |
H28B | 0.5775 | 0.2767 | 0.7893 | 0.089* | |
C29 | 0.5806 (6) | 0.3203 (3) | 0.7099 (2) | 0.0833 (17) | |
H29A | 0.6225 | 0.3649 | 0.7231 | 0.100* | |
H29B | 0.5088 | 0.3309 | 0.6802 | 0.100* | |
C30 | 0.6997 (6) | 0.2730 (3) | 0.6867 (2) | 0.0864 (17) | |
H30A | 0.7418 | 0.2964 | 0.6547 | 0.104* | |
H30B | 0.7760 | 0.2664 | 0.7153 | 0.104* | |
C31 | 0.6401 (5) | 0.2011 (2) | 0.66855 (19) | 0.0635 (14) | |
H31A | 0.7191 | 0.1717 | 0.6557 | 0.076* | |
H31B | 0.5710 | 0.2076 | 0.6372 | 0.076* | |
C32 | 0.6408 (5) | 0.0305 (2) | 0.65661 (15) | 0.0415 (11) | |
C33 | 0.7819 (5) | 0.0158 (2) | 0.67508 (16) | 0.0469 (11) | |
C34 | 0.8745 (5) | −0.0190 (2) | 0.63953 (19) | 0.0512 (12) | |
C35 | 0.6992 (6) | −0.0269 (2) | 0.57106 (18) | 0.0546 (13) | |
C36 | 0.5997 (5) | 0.0085 (2) | 0.60255 (17) | 0.0502 (12) | |
H36A | 0.5065 | 0.0176 | 0.5879 | 0.060* | |
C37 | 1.1078 (5) | −0.0689 (3) | 0.6223 (2) | 0.0925 (19) | |
H37A | 1.2005 | −0.0754 | 0.6414 | 0.139* | |
H37B | 1.1198 | −0.0408 | 0.5890 | 0.139* | |
H37C | 1.0678 | −0.1145 | 0.6121 | 0.139* | |
C38 | 0.7538 (6) | −0.0878 (3) | 0.4870 (2) | 0.0947 (19) | |
H38A | 0.7090 | −0.0999 | 0.4512 | 0.142* | |
H38B | 0.7804 | −0.1307 | 0.5069 | 0.142* | |
H38C | 0.8392 | −0.0597 | 0.4814 | 0.142* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Br1 | 0.0548 (3) | 0.0821 (4) | 0.0573 (3) | −0.0078 (3) | −0.0040 (2) | 0.0054 (3) |
P1 | 0.0562 (8) | 0.0582 (9) | 0.0455 (7) | −0.0041 (7) | 0.0065 (6) | 0.0029 (7) |
O1 | 0.081 (2) | 0.083 (3) | 0.0513 (18) | −0.006 (2) | −0.0153 (17) | 0.0075 (18) |
O2 | 0.054 (2) | 0.079 (3) | 0.063 (2) | −0.0047 (18) | −0.0001 (17) | 0.0187 (19) |
O3 | 0.060 (2) | 0.104 (3) | 0.066 (2) | −0.031 (2) | −0.0047 (18) | 0.017 (2) |
N1 | 0.043 (2) | 0.053 (3) | 0.053 (2) | 0.000 (2) | 0.0125 (19) | 0.006 (2) |
C1 | 0.061 (3) | 0.053 (3) | 0.050 (3) | −0.004 (3) | 0.016 (2) | −0.005 (3) |
C2 | 0.075 (4) | 0.066 (4) | 0.123 (5) | 0.002 (3) | 0.044 (4) | 0.002 (4) |
C3 | 0.075 (4) | 0.075 (5) | 0.136 (5) | 0.005 (4) | 0.049 (4) | 0.013 (4) |
C4 | 0.101 (5) | 0.091 (5) | 0.130 (5) | 0.032 (4) | 0.035 (4) | −0.017 (5) |
C5 | 0.144 (6) | 0.071 (4) | 0.146 (6) | −0.011 (4) | 0.091 (5) | −0.023 (4) |
C6 | 0.099 (5) | 0.071 (4) | 0.109 (4) | −0.024 (4) | 0.048 (4) | −0.034 (4) |
C7 | 0.049 (3) | 0.041 (3) | 0.045 (2) | 0.003 (2) | 0.008 (2) | 0.005 (2) |
C8 | 0.073 (4) | 0.060 (4) | 0.065 (3) | 0.005 (3) | 0.016 (3) | 0.001 (3) |
C9 | 0.073 (4) | 0.061 (4) | 0.071 (3) | 0.002 (3) | 0.005 (3) | −0.013 (3) |
C10 | 0.106 (5) | 0.050 (4) | 0.096 (4) | 0.010 (3) | 0.002 (4) | −0.006 (3) |
C11 | 0.116 (5) | 0.046 (4) | 0.079 (4) | −0.008 (3) | 0.013 (3) | 0.016 (3) |
C12 | 0.088 (4) | 0.055 (3) | 0.050 (3) | −0.002 (3) | 0.006 (3) | 0.008 (3) |
C13 | 0.048 (3) | 0.042 (3) | 0.042 (2) | 0.005 (2) | 0.009 (2) | 0.006 (2) |
C14 | 0.041 (3) | 0.048 (3) | 0.055 (3) | −0.004 (2) | 0.006 (2) | −0.002 (2) |
C15 | 0.050 (3) | 0.053 (3) | 0.047 (3) | 0.010 (3) | 0.008 (2) | 0.004 (3) |
C16 | 0.049 (3) | 0.057 (3) | 0.056 (3) | −0.005 (3) | 0.008 (3) | 0.004 (3) |
C17 | 0.053 (3) | 0.062 (3) | 0.056 (3) | −0.002 (3) | 0.003 (3) | −0.001 (3) |
C18 | 0.065 (4) | 0.110 (5) | 0.062 (3) | 0.003 (3) | 0.014 (3) | 0.032 (3) |
C19 | 0.075 (4) | 0.154 (6) | 0.072 (4) | −0.051 (4) | 0.003 (3) | 0.025 (4) |
Br2 | 0.0607 (3) | 0.0930 (4) | 0.0515 (3) | 0.0121 (3) | −0.0075 (2) | −0.0178 (3) |
P2 | 0.0424 (7) | 0.0519 (8) | 0.0427 (6) | 0.0027 (6) | 0.0061 (5) | −0.0041 (6) |
O4 | 0.0463 (19) | 0.071 (2) | 0.0546 (17) | 0.0099 (16) | −0.0003 (15) | −0.0143 (17) |
O5 | 0.051 (2) | 0.098 (3) | 0.067 (2) | 0.022 (2) | 0.0063 (17) | −0.018 (2) |
O6 | 0.094 (3) | 0.092 (3) | 0.0496 (19) | 0.033 (2) | −0.0078 (18) | −0.0273 (19) |
N2 | 0.063 (3) | 0.055 (3) | 0.043 (2) | 0.009 (2) | 0.014 (2) | −0.003 (2) |
C20 | 0.058 (3) | 0.056 (3) | 0.045 (3) | −0.009 (3) | 0.014 (2) | −0.004 (2) |
C21 | 0.084 (4) | 0.053 (4) | 0.076 (3) | 0.000 (3) | 0.023 (3) | 0.005 (3) |
C22 | 0.111 (5) | 0.066 (4) | 0.092 (4) | −0.015 (4) | 0.019 (4) | 0.021 (3) |
C23 | 0.116 (6) | 0.097 (6) | 0.101 (5) | −0.035 (4) | 0.042 (4) | 0.017 (4) |
C24 | 0.113 (6) | 0.137 (7) | 0.102 (5) | −0.012 (5) | 0.067 (4) | 0.013 (5) |
C25 | 0.086 (4) | 0.080 (4) | 0.100 (4) | 0.009 (3) | 0.059 (4) | 0.008 (3) |
C26 | 0.043 (3) | 0.047 (3) | 0.047 (2) | 0.009 (2) | 0.001 (2) | 0.002 (2) |
C27 | 0.072 (4) | 0.060 (4) | 0.064 (3) | 0.003 (3) | 0.022 (3) | −0.011 (3) |
C28 | 0.091 (4) | 0.061 (4) | 0.070 (3) | 0.013 (3) | 0.003 (3) | −0.015 (3) |
C29 | 0.091 (4) | 0.045 (4) | 0.114 (5) | 0.001 (3) | 0.004 (4) | −0.002 (3) |
C30 | 0.070 (4) | 0.062 (4) | 0.129 (5) | −0.009 (3) | 0.029 (4) | 0.004 (4) |
C31 | 0.065 (3) | 0.058 (3) | 0.070 (3) | 0.004 (3) | 0.023 (3) | 0.008 (3) |
C32 | 0.051 (3) | 0.039 (3) | 0.035 (2) | −0.001 (2) | 0.008 (2) | −0.003 (2) |
C33 | 0.048 (3) | 0.049 (3) | 0.044 (2) | 0.005 (2) | 0.007 (2) | −0.004 (2) |
C34 | 0.048 (3) | 0.052 (3) | 0.054 (3) | 0.010 (3) | 0.008 (2) | 0.008 (3) |
C35 | 0.071 (4) | 0.052 (3) | 0.041 (3) | 0.008 (3) | 0.006 (3) | −0.004 (2) |
C36 | 0.049 (3) | 0.055 (3) | 0.047 (3) | 0.009 (2) | 0.002 (2) | −0.004 (2) |
C37 | 0.057 (4) | 0.130 (5) | 0.091 (4) | 0.035 (4) | 0.014 (3) | −0.016 (4) |
C38 | 0.125 (5) | 0.107 (5) | 0.052 (3) | 0.048 (4) | 0.008 (3) | −0.023 (3) |
Br1—C14 | 1.890 (4) | Br2—C33 | 1.892 (4) |
P1—O1 | 1.479 (3) | P2—O4 | 1.482 (3) |
P1—C1 | 1.826 (4) | P2—C26 | 1.810 (4) |
P1—C7 | 1.830 (4) | P2—C20 | 1.828 (4) |
P1—C13 | 1.861 (4) | P2—C32 | 1.853 (4) |
O2—C15 | 1.342 (5) | O5—C34 | 1.347 (5) |
O2—C18 | 1.450 (5) | O5—C37 | 1.440 (5) |
O3—C16 | 1.337 (5) | O6—C35 | 1.355 (5) |
O3—C19 | 1.407 (5) | O6—C38 | 1.410 (5) |
N1—C15 | 1.322 (5) | N2—C35 | 1.323 (5) |
N1—C16 | 1.340 (5) | N2—C34 | 1.323 (5) |
C1—C2 | 1.482 (6) | C20—C21 | 1.509 (6) |
C1—C6 | 1.498 (6) | C20—C25 | 1.527 (6) |
C1—H1A | 0.9800 | C20—H20A | 0.9800 |
C2—C3 | 1.487 (7) | C21—C22 | 1.516 (6) |
C2—H2A | 0.9700 | C21—H21A | 0.9700 |
C2—H2B | 0.9700 | C21—H21B | 0.9700 |
C3—C4 | 1.491 (7) | C22—C23 | 1.517 (7) |
C3—H3A | 0.9700 | C22—H22A | 0.9700 |
C3—H3B | 0.9700 | C22—H22B | 0.9700 |
C4—C5 | 1.455 (7) | C23—C24 | 1.497 (8) |
C4—H4A | 0.9700 | C23—H23A | 0.9700 |
C4—H4B | 0.9700 | C23—H23B | 0.9700 |
C5—C6 | 1.503 (7) | C24—C25 | 1.519 (7) |
C5—H5A | 0.9700 | C24—H24A | 0.9700 |
C5—H5B | 0.9700 | C24—H24B | 0.9700 |
C6—H6A | 0.9700 | C25—H25A | 0.9700 |
C6—H6B | 0.9700 | C25—H25B | 0.9700 |
C7—C12 | 1.530 (5) | C26—C27 | 1.518 (5) |
C7—C8 | 1.532 (5) | C26—C31 | 1.520 (5) |
C7—H7A | 0.9800 | C26—H26A | 0.9800 |
C8—C9 | 1.511 (6) | C27—C28 | 1.533 (6) |
C8—H8A | 0.9700 | C27—H27A | 0.9700 |
C8—H8B | 0.9700 | C27—H27B | 0.9700 |
C9—C10 | 1.505 (6) | C28—C29 | 1.520 (6) |
C9—H9A | 0.9700 | C28—H28A | 0.9700 |
C9—H9B | 0.9700 | C28—H28B | 0.9700 |
C10—C11 | 1.520 (6) | C29—C30 | 1.528 (6) |
C10—H10A | 0.9700 | C29—H29A | 0.9700 |
C10—H10B | 0.9700 | C29—H29B | 0.9700 |
C11—C12 | 1.521 (6) | C30—C31 | 1.512 (6) |
C11—H11A | 0.9700 | C30—H30A | 0.9700 |
C11—H11B | 0.9700 | C30—H30B | 0.9700 |
C12—H12A | 0.9700 | C31—H31A | 0.9700 |
C12—H12B | 0.9700 | C31—H31B | 0.9700 |
C13—C17 | 1.349 (5) | C32—C33 | 1.384 (5) |
C13—C14 | 1.378 (5) | C32—C36 | 1.389 (5) |
C14—C15 | 1.396 (6) | C33—C34 | 1.385 (5) |
C16—C17 | 1.393 (6) | C35—C36 | 1.374 (5) |
C17—H17A | 0.9300 | C36—H36A | 0.9300 |
C18—H18A | 0.9600 | C37—H37A | 0.9600 |
C18—H18B | 0.9600 | C37—H37B | 0.9600 |
C18—H18C | 0.9600 | C37—H37C | 0.9600 |
C19—H19A | 0.9600 | C38—H38A | 0.9600 |
C19—H19B | 0.9600 | C38—H38B | 0.9600 |
C19—H19C | 0.9600 | C38—H38C | 0.9600 |
O1—P1—C1 | 114.03 (19) | O4—P2—C26 | 113.32 (19) |
O1—P1—C7 | 112.1 (2) | O4—P2—C20 | 113.00 (19) |
C1—P1—C7 | 107.6 (2) | C26—P2—C20 | 107.78 (19) |
O1—P1—C13 | 109.1 (2) | O4—P2—C32 | 107.65 (17) |
C1—P1—C13 | 104.5 (2) | C26—P2—C32 | 107.23 (19) |
C7—P1—C13 | 109.19 (18) | C20—P2—C32 | 107.56 (19) |
C15—O2—C18 | 118.7 (4) | C34—O5—C37 | 118.1 (4) |
C16—O3—C19 | 118.8 (4) | C35—O6—C38 | 117.9 (4) |
C15—N1—C16 | 118.0 (4) | C35—N2—C34 | 116.9 (4) |
C2—C1—C6 | 113.0 (4) | C21—C20—C25 | 109.5 (4) |
C2—C1—P1 | 115.0 (3) | C21—C20—P2 | 114.2 (3) |
C6—C1—P1 | 110.3 (3) | C25—C20—P2 | 109.1 (3) |
C2—C1—H1A | 105.9 | C21—C20—H20A | 107.9 |
C6—C1—H1A | 105.9 | C25—C20—H20A | 107.9 |
P1—C1—H1A | 105.9 | P2—C20—H20A | 107.9 |
C1—C2—C3 | 113.6 (4) | C20—C21—C22 | 112.7 (4) |
C1—C2—H2A | 108.8 | C20—C21—H21A | 109.1 |
C3—C2—H2A | 108.8 | C22—C21—H21A | 109.1 |
C1—C2—H2B | 108.8 | C20—C21—H21B | 109.1 |
C3—C2—H2B | 108.8 | C22—C21—H21B | 109.1 |
H2A—C2—H2B | 107.7 | H21A—C21—H21B | 107.8 |
C2—C3—C4 | 114.7 (5) | C21—C22—C23 | 111.2 (5) |
C2—C3—H3A | 108.6 | C21—C22—H22A | 109.4 |
C4—C3—H3A | 108.6 | C23—C22—H22A | 109.4 |
C2—C3—H3B | 108.6 | C21—C22—H22B | 109.4 |
C4—C3—H3B | 108.6 | C23—C22—H22B | 109.4 |
H3A—C3—H3B | 107.6 | H22A—C22—H22B | 108.0 |
C5—C4—C3 | 111.9 (5) | C24—C23—C22 | 110.4 (5) |
C5—C4—H4A | 109.2 | C24—C23—H23A | 109.6 |
C3—C4—H4A | 109.2 | C22—C23—H23A | 109.6 |
C5—C4—H4B | 109.2 | C24—C23—H23B | 109.6 |
C3—C4—H4B | 109.2 | C22—C23—H23B | 109.6 |
H4A—C4—H4B | 107.9 | H23A—C23—H23B | 108.1 |
C4—C5—C6 | 114.6 (5) | C23—C24—C25 | 113.0 (5) |
C4—C5—H5A | 108.6 | C23—C24—H24A | 109.0 |
C6—C5—H5A | 108.6 | C25—C24—H24A | 109.0 |
C4—C5—H5B | 108.6 | C23—C24—H24B | 109.0 |
C6—C5—H5B | 108.6 | C25—C24—H24B | 109.0 |
H5A—C5—H5B | 107.6 | H24A—C24—H24B | 107.8 |
C1—C6—C5 | 113.0 (5) | C24—C25—C20 | 111.5 (4) |
C1—C6—H6A | 109.0 | C24—C25—H25A | 109.3 |
C5—C6—H6A | 109.0 | C20—C25—H25A | 109.3 |
C1—C6—H6B | 109.0 | C24—C25—H25B | 109.3 |
C5—C6—H6B | 109.0 | C20—C25—H25B | 109.3 |
H6A—C6—H6B | 107.8 | H25A—C25—H25B | 108.0 |
C12—C7—C8 | 109.8 (4) | C27—C26—C31 | 110.2 (4) |
C12—C7—P1 | 108.1 (3) | C27—C26—P2 | 111.8 (3) |
C8—C7—P1 | 114.4 (3) | C31—C26—P2 | 112.2 (3) |
C12—C7—H7A | 108.1 | C27—C26—H26A | 107.4 |
C8—C7—H7A | 108.1 | C31—C26—H26A | 107.4 |
P1—C7—H7A | 108.1 | P2—C26—H26A | 107.5 |
C9—C8—C7 | 112.1 (4) | C26—C27—C28 | 111.9 (4) |
C9—C8—H8A | 109.2 | C26—C27—H27A | 109.2 |
C7—C8—H8A | 109.2 | C28—C27—H27A | 109.2 |
C9—C8—H8B | 109.2 | C26—C27—H27B | 109.2 |
C7—C8—H8B | 109.2 | C28—C27—H27B | 109.2 |
H8A—C8—H8B | 107.9 | H27A—C27—H27B | 107.9 |
C10—C9—C8 | 112.0 (4) | C29—C28—C27 | 111.1 (4) |
C10—C9—H9A | 109.2 | C29—C28—H28A | 109.4 |
C8—C9—H9A | 109.2 | C27—C28—H28A | 109.4 |
C10—C9—H9B | 109.2 | C29—C28—H28B | 109.4 |
C8—C9—H9B | 109.2 | C27—C28—H28B | 109.4 |
H9A—C9—H9B | 107.9 | H28A—C28—H28B | 108.0 |
C9—C10—C11 | 110.6 (4) | C28—C29—C30 | 110.2 (4) |
C9—C10—H10A | 109.5 | C28—C29—H29A | 109.6 |
C11—C10—H10A | 109.5 | C30—C29—H29A | 109.6 |
C9—C10—H10B | 109.5 | C28—C29—H29B | 109.6 |
C11—C10—H10B | 109.5 | C30—C29—H29B | 109.6 |
H10A—C10—H10B | 108.1 | H29A—C29—H29B | 108.1 |
C12—C11—C10 | 112.3 (4) | C31—C30—C29 | 111.3 (4) |
C12—C11—H11A | 109.1 | C31—C30—H30A | 109.4 |
C10—C11—H11A | 109.1 | C29—C30—H30A | 109.4 |
C12—C11—H11B | 109.1 | C31—C30—H30B | 109.4 |
C10—C11—H11B | 109.1 | C29—C30—H30B | 109.4 |
H11A—C11—H11B | 107.9 | H30A—C30—H30B | 108.0 |
C11—C12—C7 | 111.2 (3) | C30—C31—C26 | 112.2 (4) |
C11—C12—H12A | 109.4 | C30—C31—H31A | 109.2 |
C7—C12—H12A | 109.4 | C26—C31—H31A | 109.2 |
C11—C12—H12B | 109.4 | C30—C31—H31B | 109.2 |
C7—C12—H12B | 109.4 | C26—C31—H31B | 109.2 |
H12A—C12—H12B | 108.0 | H31A—C31—H31B | 107.9 |
C17—C13—C14 | 119.3 (4) | C33—C32—C36 | 117.1 (4) |
C17—C13—P1 | 113.9 (3) | C33—C32—P2 | 128.7 (3) |
C14—C13—P1 | 126.8 (4) | C36—C32—P2 | 114.1 (3) |
C13—C14—C15 | 118.9 (4) | C32—C33—C34 | 119.4 (4) |
C13—C14—Br1 | 124.0 (3) | C32—C33—Br2 | 122.7 (3) |
C15—C14—Br1 | 117.1 (3) | C34—C33—Br2 | 117.9 (3) |
N1—C15—O2 | 119.0 (4) | N2—C34—O5 | 118.9 (4) |
N1—C15—C14 | 122.2 (4) | N2—C34—C33 | 123.3 (4) |
O2—C15—C14 | 118.8 (4) | O5—C34—C33 | 117.7 (4) |
O3—C16—N1 | 118.4 (4) | N2—C35—O6 | 118.3 (4) |
O3—C16—C17 | 118.8 (4) | N2—C35—C36 | 124.3 (4) |
N1—C16—C17 | 122.7 (4) | O6—C35—C36 | 117.3 (5) |
C13—C17—C16 | 118.8 (4) | C35—C36—C32 | 118.8 (4) |
C13—C17—H17A | 120.6 | C35—C36—H36A | 120.6 |
C16—C17—H17A | 120.6 | C32—C36—H36A | 120.6 |
O2—C18—H18A | 109.5 | O5—C37—H37A | 109.5 |
O2—C18—H18B | 109.5 | O5—C37—H37B | 109.5 |
H18A—C18—H18B | 109.5 | H37A—C37—H37B | 109.5 |
O2—C18—H18C | 109.5 | O5—C37—H37C | 109.5 |
H18A—C18—H18C | 109.5 | H37A—C37—H37C | 109.5 |
H18B—C18—H18C | 109.5 | H37B—C37—H37C | 109.5 |
O3—C19—H19A | 109.5 | O6—C38—H38A | 109.5 |
O3—C19—H19B | 109.5 | O6—C38—H38B | 109.5 |
H19A—C19—H19B | 109.5 | H38A—C38—H38B | 109.5 |
O3—C19—H19C | 109.5 | O6—C38—H38C | 109.5 |
H19A—C19—H19C | 109.5 | H38A—C38—H38C | 109.5 |
H19B—C19—H19C | 109.5 | H38B—C38—H38C | 109.5 |
O1—P1—C1—C2 | 73.2 (4) | O4—P2—C20—C21 | 88.4 (4) |
C7—P1—C1—C2 | −51.8 (4) | C26—P2—C20—C21 | −145.6 (3) |
C13—P1—C1—C2 | −167.8 (4) | C32—P2—C20—C21 | −30.3 (4) |
O1—P1—C1—C6 | −55.9 (4) | O4—P2—C20—C25 | −34.5 (4) |
C7—P1—C1—C6 | 179.1 (3) | C26—P2—C20—C25 | 91.5 (4) |
C13—P1—C1—C6 | 63.1 (4) | C32—P2—C20—C25 | −153.2 (3) |
C6—C1—C2—C3 | −47.0 (7) | C25—C20—C21—C22 | −55.6 (6) |
P1—C1—C2—C3 | −174.8 (4) | P2—C20—C21—C22 | −178.2 (3) |
C1—C2—C3—C4 | 48.5 (7) | C20—C21—C22—C23 | 56.5 (6) |
C2—C3—C4—C5 | −49.2 (8) | C21—C22—C23—C24 | −54.4 (7) |
C3—C4—C5—C6 | 49.6 (8) | C22—C23—C24—C25 | 54.5 (7) |
C2—C1—C6—C5 | 47.2 (7) | C23—C24—C25—C20 | −55.0 (7) |
P1—C1—C6—C5 | 177.5 (4) | C21—C20—C25—C24 | 54.0 (6) |
C4—C5—C6—C1 | −49.6 (8) | P2—C20—C25—C24 | 179.6 (4) |
O1—P1—C7—C12 | −36.3 (4) | O4—P2—C26—C27 | 52.7 (3) |
C1—P1—C7—C12 | 89.9 (3) | C20—P2—C26—C27 | −73.1 (3) |
C13—P1—C7—C12 | −157.3 (3) | C32—P2—C26—C27 | 171.4 (3) |
O1—P1—C7—C8 | 86.4 (3) | O4—P2—C26—C31 | −71.7 (3) |
C1—P1—C7—C8 | −147.5 (3) | C20—P2—C26—C31 | 162.5 (3) |
C13—P1—C7—C8 | −34.6 (4) | C32—P2—C26—C31 | 47.0 (3) |
C12—C7—C8—C9 | −55.0 (5) | C31—C26—C27—C28 | −54.6 (5) |
P1—C7—C8—C9 | −176.7 (3) | P2—C26—C27—C28 | 179.9 (3) |
C7—C8—C9—C10 | 55.9 (5) | C26—C27—C28—C29 | 56.0 (5) |
C8—C9—C10—C11 | −54.7 (6) | C27—C28—C29—C30 | −55.7 (6) |
C9—C10—C11—C12 | 55.0 (6) | C28—C29—C30—C31 | 56.1 (6) |
C10—C11—C12—C7 | −55.6 (6) | C29—C30—C31—C26 | −56.3 (6) |
C8—C7—C12—C11 | 54.5 (5) | C27—C26—C31—C30 | 55.0 (5) |
P1—C7—C12—C11 | 180.0 (4) | P2—C26—C31—C30 | −179.7 (3) |
O1—P1—C13—C17 | 6.2 (4) | O4—P2—C32—C33 | 177.9 (4) |
C1—P1—C13—C17 | −116.1 (3) | C26—P2—C32—C33 | 55.7 (4) |
C7—P1—C13—C17 | 129.0 (3) | C20—P2—C32—C33 | −60.0 (4) |
O1—P1—C13—C14 | −176.4 (4) | O4—P2—C32—C36 | −2.0 (4) |
C1—P1—C13—C14 | 61.3 (4) | C26—P2—C32—C36 | −124.2 (3) |
C7—P1—C13—C14 | −53.6 (4) | C20—P2—C32—C36 | 120.1 (3) |
C17—C13—C14—C15 | −1.4 (6) | C36—C32—C33—C34 | 0.4 (6) |
P1—C13—C14—C15 | −178.6 (3) | P2—C32—C33—C34 | −179.5 (3) |
C17—C13—C14—Br1 | 176.4 (3) | C36—C32—C33—Br2 | 179.2 (3) |
P1—C13—C14—Br1 | −0.9 (6) | P2—C32—C33—Br2 | −0.7 (6) |
C16—N1—C15—O2 | −179.5 (4) | C35—N2—C34—O5 | 179.7 (4) |
C16—N1—C15—C14 | 0.1 (6) | C35—N2—C34—C33 | 1.9 (7) |
C18—O2—C15—N1 | 5.2 (6) | C37—O5—C34—N2 | 2.2 (6) |
C18—O2—C15—C14 | −174.4 (4) | C37—O5—C34—C33 | −179.9 (4) |
C13—C14—C15—N1 | 1.8 (7) | C32—C33—C34—N2 | −1.8 (7) |
Br1—C14—C15—N1 | −176.1 (3) | Br2—C33—C34—N2 | 179.3 (3) |
C13—C14—C15—O2 | −178.6 (4) | C32—C33—C34—O5 | −179.7 (4) |
Br1—C14—C15—O2 | 3.5 (5) | Br2—C33—C34—O5 | 1.4 (6) |
C19—O3—C16—N1 | −4.2 (7) | C34—N2—C35—O6 | 179.5 (4) |
C19—O3—C16—C17 | 175.4 (5) | C34—N2—C35—C36 | −0.6 (7) |
C15—N1—C16—O3 | 177.3 (4) | C38—O6—C35—N2 | 2.9 (7) |
C15—N1—C16—C17 | −2.4 (7) | C38—O6—C35—C36 | −177.0 (4) |
C14—C13—C17—C16 | −0.8 (7) | N2—C35—C36—C32 | −0.8 (7) |
P1—C13—C17—C16 | 176.8 (3) | O6—C35—C36—C32 | 179.2 (4) |
O3—C16—C17—C13 | −176.9 (4) | C33—C32—C36—C35 | 0.8 (6) |
N1—C16—C17—C13 | 2.8 (7) | P2—C32—C36—C35 | −179.3 (3) |
Experimental details
Crystal data | |
Chemical formula | C19H29BrNO3P |
Mr | 430.31 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 294 |
a, b, c (Å) | 9.2025 (12), 18.759 (2), 23.761 (3) |
β (°) | 92.009 (3) |
V (Å3) | 4099.3 (9) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 2.10 |
Crystal size (mm) | 0.30 × 0.26 × 0.24 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.571, 0.633 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 27403, 9427, 3936 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.651 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.117, 1.03 |
No. of reflections | 9427 |
No. of parameters | 451 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.91, −0.60 |
Computer programs: SMART (Siemens, 1995), SMART, SHELXTL-NT (Siemens, 1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL-NT.
The search for new chiral ligands is an ongoing process in the field of asymmetric synthesis. Over the past two decades, tremendous success has been achieved in the use of chiral arylphosphine ligands such as BINAP, BIPHEP, DuPhos, and so on, in Rh- or Ru-catalyzed asymmetric hydrogenation reactions (Lin et al., 2001). As an effort to expand the scope of the arylphosphine ligands and their application in homogeneous asymmetric catalysis, we have recently developed a class of novel dipyridylphosphine ligands P-Phos (Pai et al., 2000) and Tol-P-Phos (Wu et al., 2001), and found their RuII complexes to be highly effective in the catalytic asymmetric hydrogenation of 2-(6-methoxy-2-naphthyl)propenoic acid and keto esters. [Please define BINAP, BIPHEP, DuPhos, P-Phos and Tol-P-Phos]
In this study, we attempt to synthesize another new P-Phos derivative, namely 2,2',6,6'-tetramethoxy-4,4'-bis(dicyclohexylphosphino)-3,3'-bipyridine, (II), by replacing the four phenyl rings in P-Phos with four cyclohexyl rings as a means to tune its electronic and steric properties. In the synthesis of the target product, the title compound, (I), is the important intermediate, which was obtained by the ortho-lithiation of 3-bromo-2,6-dimethoxypyridine with lithium diisopropylamide (LDA), followed by the addition of dicyclohexylphosphine chloride and then by oxidation of resulted phosphine with hydrogen peroxide.
Among these procedures, the ortho-lithiation reaction deserves further comment. Regioselective lithiation of halopyridines always occurred lithium–halogen exchange, halogen-dancing reaction or deprotonation reaction. The choice of lithium reagent (i.e. n-Bu—Li or LDA) is also very important (Rocca et al., 1993). The relative kinetic acidity of pyridine (C-4 > C-3 > C-2; Zoltewica et al., 1969) combined with the greatly increased kinetic acidity of the ortho H atom in halobenzenes suggested that it would be feasible to metalate regioselectively the C-4 position of 3-halopyridines. The X-ray crystallographic analysis of (I) unambiguously showed that the ortho-lithiation reaction proceeds with high chemo- and regioselectivity and is almost avoid the formation of by-products. By well defined intermolecular weak interactions, molecules of (I) (as building blocks) were finally assemblied into three-dimensional network. As part of our efforts investigating this domain, we present the crystal structure of (I). The synthesis of chiral ligand (II) and its application in the Ru- or Rh-catalyzed asymmetric hydrogenation reactions are underway.