A carbohydrate-derived optically active P-chiral dioxophenylphospholane–borane complex, C27H32BO6P, was prepared from bis(diethylamino)phenylphosphine and methyl 2,6-di-O-benzyl-β-D-galactopyranoside. The phosphinite was prepared with high diastereoselectivity and in good yield. The absolute configuration (R) at the P atom was deduced from the known configuration of the sugar moiety. Weak intermolecular interactions link the molecules into a three-dimensional network.
Supporting information
CCDC reference: 241222
Bis(diethylamino)phenylphosphine (151.4 mg, 0.5 mmol) and methyl-O-(2,6-dibenzyl)-β-D-galactopyranoside (187.1 mg, 0.5 mmol) were dissolved in toluene (10 ml). The resulting mixture was then refluxed under an Ar atmosphere until no evolution of diethylamine could be detected by the use of a pH indicator (approximately 16 h). The solution was then cooled to 273 K and BH3·DMS (0.3 ml, 0.6 mmol) was added dropwise by syringe. After stirring for an additional 16 h at ambient temperature, the reaction mixture was concentrated under reduced pressure to yield a colourless syrup. The syrup was dissolved in and crystallized from 2-propanol by slow evaporation.
Approximately 8% of the collected data were removed due to bad background. The poor quality also results in an unusually high Rint of 0.142. The absolute configuration could not be determined from the diffraction data, because of the high uncertainty (0.4) in the Flack (1983) parameter, but was assigned by the known configuration of the carbohydrate moiety. H atoms were placed in calculated positions and refined riding on their carrier atoms at distances of 0.93, 0.96, 0.96, 0.97 and 0.98 Å for aromatic, borane, methyl, methylene and methine C—H, respectively, and with Uiso(H) = xUeq(C, B), where x = 1.5 for methyl and borane H atoms and 1.2 for all others.
Data collection: CAD-4 EXPRESS (Enraf Nonius, 1994); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997).
Methyl 2,6-di-
O-benzyl-3,4-
O-phenylphosphinediyl-
β-
D-galactopyranoside (P—B)borane
top
Crystal data top
C27H32BO6P | F(000) = 524 |
Mr = 494.32 | Dx = 1.213 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 10.7567 (19) Å | Cell parameters from 19 reflections |
b = 9.800 (9) Å | θ = 11.1–15.3° |
c = 12.926 (4) Å | µ = 0.14 mm−1 |
β = 96.63 (2)° | T = 293 K |
V = 1353.6 (13) Å3 | Rod, colourless |
Z = 2 | 0.55 × 0.25 × 0.10 mm |
Data collection top
Enraf-Nonius CAD-4 diffractometer | θmax = 27.0°, θmin = 2.3° |
non–profiled ω/2θ scans | h = −13→13 |
5762 measured reflections | k = −12→0 |
3105 independent reflections | l = −16→16 |
1621 reflections with I > 2σ(I) | 3 standard reflections every 120 min |
Rint = 0.142 | intensity decay: none |
Refinement top
Refinement on F2 | H-atom parameters constrained |
Least-squares matrix: full | w = 1/[σ2(Fo2) + (0.0668P)2] where P = (Fo2 + 2Fc2)/3 |
R[F2 > 2σ(F2)] = 0.048 | (Δ/σ)max = 0.001 |
wR(F2) = 0.144 | Δρmax = 0.26 e Å−3 |
S = 1.04 | Δρmin = −0.22 e Å−3 |
3105 reflections | Absolute structure: (Flack, 1983) |
319 parameters | Absolute structure parameter: 0.0 (4) |
1 restraint | |
Crystal data top
C27H32BO6P | V = 1353.6 (13) Å3 |
Mr = 494.32 | Z = 2 |
Monoclinic, P21 | Mo Kα radiation |
a = 10.7567 (19) Å | µ = 0.14 mm−1 |
b = 9.800 (9) Å | T = 293 K |
c = 12.926 (4) Å | 0.55 × 0.25 × 0.10 mm |
β = 96.63 (2)° | |
Data collection top
Enraf-Nonius CAD-4 diffractometer | Rint = 0.142 |
5762 measured reflections | 3 standard reflections every 120 min |
3105 independent reflections | intensity decay: none |
1621 reflections with I > 2σ(I) | |
Refinement top
R[F2 > 2σ(F2)] = 0.048 | H-atom parameters constrained |
wR(F2) = 0.144 | Δρmax = 0.26 e Å−3 |
S = 1.04 | Δρmin = −0.22 e Å−3 |
3105 reflections | Absolute structure: (Flack, 1983) |
319 parameters | Absolute structure parameter: 0.0 (4) |
1 restraint | |
Special details top
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. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.5235 (4) | 0.2634 (5) | −0.1040 (3) | 0.0570 (10) | |
H1 | 0.5577 | 0.3515 | −0.1228 | 0.068* | |
C2 | 0.3968 (4) | 0.2826 (4) | −0.0643 (3) | 0.0554 (10) | |
H2 | 0.3590 | 0.1933 | −0.0544 | 0.067* | |
C3 | 0.4123 (4) | 0.3596 (4) | 0.0381 (3) | 0.0578 (10) | |
H3 | 0.4206 | 0.4574 | 0.0246 | 0.069* | |
C4 | 0.5218 (4) | 0.3120 (4) | 0.1138 (3) | 0.0530 (9) | |
H4 | 0.5419 | 0.3811 | 0.1680 | 0.064* | |
C5 | 0.6372 (3) | 0.2779 (4) | 0.0630 (3) | 0.0520 (9) | |
H5 | 0.6756 | 0.3632 | 0.0431 | 0.062* | |
C6 | 0.7324 (4) | 0.1990 (5) | 0.1326 (3) | 0.0586 (10) | |
H6A | 0.7013 | 0.1080 | 0.1440 | 0.070* | |
H6B | 0.8092 | 0.1908 | 0.1004 | 0.070* | |
C7 | 0.6079 (5) | 0.1774 (7) | −0.2531 (4) | 0.0905 (18) | |
H7A | 0.5836 | 0.1293 | −0.3168 | 0.136* | |
H7B | 0.6790 | 0.1331 | −0.2156 | 0.136* | |
H7C | 0.6295 | 0.2697 | −0.2685 | 0.136* | |
C8 | 0.2375 (4) | 0.2849 (6) | −0.2106 (3) | 0.0730 (13) | |
H8A | 0.2875 | 0.2161 | −0.2404 | 0.088* | |
H8B | 0.2042 | 0.3456 | −0.2663 | 0.088* | |
C9 | 0.1311 (4) | 0.2167 (5) | −0.1664 (3) | 0.0584 (10) | |
C10 | 0.1219 (5) | 0.0742 (6) | −0.1658 (4) | 0.0753 (14) | |
H10 | 0.1835 | 0.0211 | −0.1908 | 0.090* | |
C11 | 0.0203 (6) | 0.0128 (5) | −0.1277 (5) | 0.0909 (17) | |
H11 | 0.0142 | −0.0819 | −0.1282 | 0.109* | |
C12 | −0.0704 (6) | 0.0876 (6) | −0.0899 (5) | 0.0863 (16) | |
H12 | −0.1384 | 0.0450 | −0.0651 | 0.104* | |
C13 | −0.0603 (5) | 0.2288 (7) | −0.0886 (4) | 0.0796 (14) | |
H13 | −0.1210 | 0.2821 | −0.0624 | 0.096* | |
C14 | 0.0395 (5) | 0.2882 (5) | −0.1263 (4) | 0.0717 (13) | |
H14 | 0.0455 | 0.3829 | −0.1245 | 0.086* | |
C15 | 0.8442 (5) | 0.2024 (7) | 0.2977 (4) | 0.0887 (15) | |
H15A | 0.9247 | 0.2048 | 0.2707 | 0.106* | |
H15B | 0.8202 | 0.1076 | 0.3036 | 0.106* | |
C16 | 0.8561 (5) | 0.2681 (7) | 0.4039 (4) | 0.0737 (13) | |
C17 | 0.9284 (6) | 0.2069 (10) | 0.4829 (5) | 0.113 (2) | |
H17 | 0.9708 | 0.1272 | 0.4698 | 0.135* | |
C18 | 0.9407 (9) | 0.2585 (13) | 0.5806 (6) | 0.144 (4) | |
H18 | 0.9897 | 0.2130 | 0.6337 | 0.172* | |
C19 | 0.8824 (8) | 0.3755 (13) | 0.6015 (6) | 0.128 (3) | |
H19 | 0.8928 | 0.4125 | 0.6682 | 0.154* | |
C20 | 0.8098 (8) | 0.4370 (11) | 0.5251 (7) | 0.128 (3) | |
H20 | 0.7683 | 0.5168 | 0.5394 | 0.153* | |
C21 | 0.7943 (6) | 0.3845 (8) | 0.4239 (5) | 0.103 (2) | |
H21 | 0.7429 | 0.4283 | 0.3714 | 0.124* | |
C22 | 0.3378 (5) | 0.2915 (5) | 0.3037 (4) | 0.0740 (13) | |
C23 | 0.4468 (6) | 0.2963 (10) | 0.3691 (4) | 0.116 (3) | |
H23 | 0.5199 | 0.2629 | 0.3463 | 0.139* | |
C24 | 0.4513 (8) | 0.3507 (14) | 0.4703 (5) | 0.154 (4) | |
H24 | 0.5262 | 0.3542 | 0.5140 | 0.185* | |
C25 | 0.3456 (11) | 0.3970 (15) | 0.5022 (7) | 0.164 (5) | |
H25 | 0.3468 | 0.4314 | 0.5693 | 0.197* | |
C26 | 0.2362 (11) | 0.3948 (11) | 0.4383 (8) | 0.152 (4) | |
H26 | 0.1634 | 0.4289 | 0.4612 | 0.182* | |
C27 | 0.2335 (6) | 0.3416 (9) | 0.3389 (5) | 0.110 (2) | |
H27 | 0.1583 | 0.3403 | 0.2954 | 0.133* | |
O1 | 0.5062 (3) | 0.1777 (3) | −0.1908 (2) | 0.0698 (9) | |
O2 | 0.3157 (3) | 0.3610 (3) | −0.1351 (2) | 0.0676 (8) | |
O3 | 0.3036 (3) | 0.3364 (3) | 0.0936 (2) | 0.0656 (8) | |
O4 | 0.4739 (3) | 0.1896 (3) | 0.1592 (2) | 0.0590 (7) | |
O5 | 0.6075 (2) | 0.1969 (3) | −0.0281 (2) | 0.0553 (7) | |
O6 | 0.7558 (3) | 0.2689 (3) | 0.2285 (2) | 0.0643 (8) | |
P1 | 0.33112 (10) | 0.21660 (13) | 0.17683 (10) | 0.0638 (3) | |
B1 | 0.2263 (6) | 0.0669 (7) | 0.1569 (6) | 0.090 (2) | |
HA | 0.1425 | 0.0935 | 0.1665 | 0.135* | |
HB | 0.2542 | −0.0029 | 0.2063 | 0.135* | |
HC | 0.2277 | 0.0325 | 0.0875 | 0.135* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
C1 | 0.066 (2) | 0.0489 (19) | 0.056 (2) | −0.008 (2) | 0.0065 (19) | −0.002 (2) |
C2 | 0.058 (2) | 0.0422 (18) | 0.064 (2) | 0.001 (2) | 0.0016 (18) | 0.010 (2) |
C3 | 0.065 (2) | 0.045 (2) | 0.064 (3) | 0.006 (2) | 0.009 (2) | 0.006 (2) |
C4 | 0.064 (2) | 0.0415 (18) | 0.054 (2) | −0.0044 (19) | 0.0064 (19) | 0.0002 (19) |
C5 | 0.056 (2) | 0.0448 (18) | 0.055 (2) | −0.006 (2) | 0.0053 (17) | −0.004 (2) |
C6 | 0.060 (2) | 0.056 (2) | 0.060 (2) | 0.003 (2) | 0.0076 (18) | −0.003 (2) |
C7 | 0.092 (3) | 0.109 (5) | 0.072 (3) | −0.005 (4) | 0.018 (3) | −0.014 (4) |
C8 | 0.068 (3) | 0.087 (3) | 0.061 (3) | −0.002 (3) | −0.005 (2) | 0.007 (3) |
C9 | 0.059 (2) | 0.059 (2) | 0.054 (2) | 0.004 (3) | −0.0057 (18) | 0.000 (2) |
C10 | 0.082 (3) | 0.062 (3) | 0.079 (3) | 0.018 (3) | −0.003 (3) | −0.004 (3) |
C11 | 0.109 (4) | 0.053 (3) | 0.105 (4) | −0.014 (3) | −0.010 (4) | 0.006 (3) |
C12 | 0.079 (3) | 0.073 (3) | 0.106 (4) | −0.020 (3) | 0.007 (3) | −0.001 (3) |
C13 | 0.069 (3) | 0.085 (3) | 0.086 (3) | 0.006 (3) | 0.017 (3) | −0.001 (3) |
C14 | 0.081 (3) | 0.056 (3) | 0.078 (3) | −0.002 (3) | 0.009 (3) | −0.006 (3) |
C15 | 0.093 (3) | 0.091 (4) | 0.076 (3) | 0.020 (4) | −0.016 (2) | 0.004 (4) |
C16 | 0.077 (3) | 0.084 (3) | 0.058 (3) | −0.009 (3) | 0.000 (2) | −0.001 (3) |
C17 | 0.126 (5) | 0.116 (5) | 0.087 (4) | −0.001 (6) | −0.029 (3) | 0.007 (5) |
C18 | 0.176 (8) | 0.172 (10) | 0.071 (4) | −0.026 (8) | −0.040 (4) | 0.003 (6) |
C19 | 0.143 (7) | 0.175 (9) | 0.066 (4) | −0.036 (8) | 0.009 (4) | −0.027 (6) |
C20 | 0.133 (6) | 0.144 (7) | 0.108 (5) | −0.016 (6) | 0.022 (5) | −0.044 (6) |
C21 | 0.112 (5) | 0.111 (5) | 0.087 (4) | 0.012 (5) | 0.009 (3) | −0.017 (4) |
C22 | 0.076 (3) | 0.070 (3) | 0.080 (3) | 0.003 (3) | 0.025 (3) | 0.010 (3) |
C23 | 0.110 (4) | 0.166 (8) | 0.074 (3) | 0.021 (6) | 0.020 (3) | 0.003 (5) |
C24 | 0.151 (7) | 0.233 (12) | 0.080 (4) | −0.012 (9) | 0.022 (4) | −0.010 (7) |
C25 | 0.178 (8) | 0.227 (13) | 0.097 (5) | −0.037 (10) | 0.058 (6) | −0.043 (8) |
C26 | 0.164 (8) | 0.161 (9) | 0.147 (7) | 0.009 (8) | 0.087 (7) | −0.041 (8) |
C27 | 0.104 (4) | 0.122 (5) | 0.112 (4) | −0.001 (5) | 0.042 (4) | −0.018 (5) |
O1 | 0.0709 (17) | 0.076 (2) | 0.0624 (17) | −0.0056 (18) | 0.0049 (14) | −0.0139 (18) |
O2 | 0.0684 (18) | 0.0516 (16) | 0.079 (2) | −0.0038 (17) | −0.0066 (15) | 0.0105 (17) |
O3 | 0.0620 (16) | 0.0646 (17) | 0.0717 (18) | 0.0172 (16) | 0.0145 (14) | 0.0099 (17) |
O4 | 0.0605 (15) | 0.0494 (15) | 0.0691 (17) | 0.0049 (15) | 0.0167 (13) | 0.0117 (15) |
O5 | 0.0581 (14) | 0.0505 (15) | 0.0570 (15) | −0.0012 (15) | 0.0056 (12) | −0.0036 (15) |
O6 | 0.0709 (17) | 0.0566 (15) | 0.0622 (17) | 0.0000 (17) | −0.0060 (14) | −0.0046 (16) |
P1 | 0.0609 (6) | 0.0591 (6) | 0.0745 (7) | 0.0037 (6) | 0.0204 (5) | 0.0064 (7) |
B1 | 0.078 (4) | 0.072 (3) | 0.124 (5) | −0.013 (4) | 0.033 (4) | 0.001 (4) |
Geometric parameters (Å, º) top
C1—O1 | 1.396 (5) | C13—H13 | 0.9300 |
C1—O5 | 1.414 (5) | C14—H14 | 0.9300 |
C1—C2 | 1.522 (5) | C15—O6 | 1.390 (6) |
C1—H1 | 0.9800 | C15—C16 | 1.509 (7) |
C2—O2 | 1.415 (5) | C15—H15A | 0.9700 |
C2—C3 | 1.516 (6) | C15—H15B | 0.9700 |
C2—H2 | 0.9800 | C16—C17 | 1.350 (8) |
C3—O3 | 1.458 (4) | C16—C21 | 1.360 (9) |
C3—C4 | 1.516 (6) | C17—C18 | 1.352 (10) |
C3—H3 | 0.9800 | C17—H17 | 0.9300 |
C4—O4 | 1.457 (4) | C18—C19 | 1.349 (14) |
C4—C5 | 1.507 (5) | C18—H18 | 0.9300 |
C4—H4 | 0.9800 | C19—C20 | 1.331 (12) |
C5—O5 | 1.426 (5) | C19—H19 | 0.9300 |
C5—C6 | 1.498 (6) | C20—C21 | 1.397 (9) |
C5—H5 | 0.9800 | C20—H20 | 0.9300 |
C6—O6 | 1.414 (5) | C21—H21 | 0.9300 |
C6—H6A | 0.9700 | C22—C27 | 1.351 (7) |
C6—H6B | 0.9700 | C22—C23 | 1.365 (8) |
C7—O1 | 1.431 (5) | C22—P1 | 1.790 (5) |
C7—H7A | 0.9600 | C23—C24 | 1.409 (10) |
C7—H7B | 0.9600 | C23—H23 | 0.9300 |
C7—H7C | 0.9600 | C24—C25 | 1.332 (12) |
C8—O2 | 1.424 (6) | C24—H24 | 0.9300 |
C8—C9 | 1.494 (6) | C25—C26 | 1.358 (12) |
C8—H8A | 0.9700 | C25—H25 | 0.9300 |
C8—H8B | 0.9700 | C26—C27 | 1.384 (11) |
C9—C14 | 1.360 (6) | C26—H26 | 0.9300 |
C9—C10 | 1.399 (7) | C27—H27 | 0.9300 |
C10—C11 | 1.387 (8) | O3—P1 | 1.597 (3) |
C10—H10 | 0.9300 | O4—P1 | 1.600 (3) |
C11—C12 | 1.357 (8) | P1—B1 | 1.851 (6) |
C11—H11 | 0.9300 | B1—HA | 0.9600 |
C12—C13 | 1.388 (9) | B1—HB | 0.9600 |
C12—H12 | 0.9300 | B1—HC | 0.9600 |
C13—C14 | 1.360 (7) | | |
| | | |
O1—C1—O5 | 107.2 (3) | C9—C14—C13 | 123.6 (5) |
O1—C1—C2 | 107.7 (3) | C9—C14—H14 | 118.2 |
O5—C1—C2 | 110.4 (3) | C13—C14—H14 | 118.2 |
O1—C1—H1 | 110.5 | O6—C15—C16 | 111.4 (5) |
O5—C1—H1 | 110.5 | O6—C15—H15A | 109.3 |
C2—C1—H1 | 110.5 | C16—C15—H15A | 109.3 |
O2—C2—C3 | 107.0 (3) | O6—C15—H15B | 109.3 |
O2—C2—C1 | 111.0 (3) | C16—C15—H15B | 109.3 |
C3—C2—C1 | 110.1 (3) | H15A—C15—H15B | 108.0 |
O2—C2—H2 | 109.6 | C17—C16—C21 | 118.7 (6) |
C3—C2—H2 | 109.6 | C17—C16—C15 | 118.7 (6) |
C1—C2—H2 | 109.6 | C21—C16—C15 | 122.6 (5) |
O3—C3—C2 | 109.8 (3) | C16—C17—C18 | 121.8 (9) |
O3—C3—C4 | 104.0 (3) | C16—C17—H17 | 119.1 |
C2—C3—C4 | 114.2 (3) | C18—C17—H17 | 119.1 |
O3—C3—H3 | 109.6 | C17—C18—C19 | 120.4 (9) |
C2—C3—H3 | 109.6 | C17—C18—H18 | 119.8 |
C4—C3—H3 | 109.6 | C19—C18—H18 | 119.8 |
O4—C4—C5 | 109.9 (3) | C20—C19—C18 | 118.9 (8) |
O4—C4—C3 | 103.2 (3) | C20—C19—H19 | 120.6 |
C5—C4—C3 | 113.9 (3) | C18—C19—H19 | 120.6 |
O4—C4—H4 | 109.9 | C19—C20—C21 | 121.6 (9) |
C5—C4—H4 | 109.9 | C19—C20—H20 | 119.2 |
C3—C4—H4 | 109.9 | C21—C20—H20 | 119.2 |
O5—C5—C6 | 106.3 (3) | C16—C21—C20 | 118.6 (7) |
O5—C5—C4 | 111.5 (3) | C16—C21—H21 | 120.7 |
C6—C5—C4 | 113.2 (3) | C20—C21—H21 | 120.7 |
O5—C5—H5 | 108.6 | C27—C22—C23 | 117.8 (6) |
C6—C5—H5 | 108.6 | C27—C22—P1 | 120.7 (5) |
C4—C5—H5 | 108.6 | C23—C22—P1 | 121.5 (4) |
O6—C6—C5 | 108.4 (3) | C22—C23—C24 | 121.5 (7) |
O6—C6—H6A | 110.0 | C22—C23—H23 | 119.2 |
C5—C6—H6A | 110.0 | C24—C23—H23 | 119.2 |
O6—C6—H6B | 110.0 | C25—C24—C23 | 118.5 (8) |
C5—C6—H6B | 110.0 | C25—C24—H24 | 120.8 |
H6A—C6—H6B | 108.4 | C23—C24—H24 | 120.8 |
O1—C7—H7A | 109.5 | C24—C25—C26 | 121.2 (8) |
O1—C7—H7B | 109.5 | C24—C25—H25 | 119.4 |
H7A—C7—H7B | 109.5 | C26—C25—H25 | 119.4 |
O1—C7—H7C | 109.5 | C25—C26—C27 | 119.6 (8) |
H7A—C7—H7C | 109.5 | C25—C26—H26 | 120.2 |
H7B—C7—H7C | 109.5 | C27—C26—H26 | 120.2 |
O2—C8—C9 | 113.0 (3) | C22—C27—C26 | 121.4 (7) |
O2—C8—H8A | 109.0 | C22—C27—H27 | 119.3 |
C9—C8—H8A | 109.0 | C26—C27—H27 | 119.3 |
O2—C8—H8B | 109.0 | C1—O1—C7 | 114.4 (4) |
C9—C8—H8B | 109.0 | C2—O2—C8 | 115.5 (4) |
H8A—C8—H8B | 107.8 | C3—O3—P1 | 110.4 (2) |
C14—C9—C10 | 117.2 (5) | C4—O4—P1 | 108.1 (2) |
C14—C9—C8 | 122.4 (5) | C1—O5—C5 | 112.4 (3) |
C10—C9—C8 | 120.5 (5) | C15—O6—C6 | 112.1 (4) |
C11—C10—C9 | 119.7 (5) | O3—P1—O4 | 97.59 (14) |
C11—C10—H10 | 120.2 | O3—P1—C22 | 107.5 (2) |
C9—C10—H10 | 120.2 | O4—P1—C22 | 105.1 (2) |
C12—C11—C10 | 121.5 (5) | O3—P1—B1 | 115.2 (3) |
C12—C11—H11 | 119.3 | O4—P1—B1 | 115.4 (2) |
C10—C11—H11 | 119.3 | C22—P1—B1 | 114.3 (3) |
C11—C12—C13 | 119.0 (5) | P1—B1—HA | 109.5 |
C11—C12—H12 | 120.5 | P1—B1—HB | 109.5 |
C13—C12—H12 | 120.5 | HA—B1—HB | 109.5 |
C14—C13—C12 | 119.1 (5) | P1—B1—HC | 109.5 |
C14—C13—H13 | 120.4 | HA—B1—HC | 109.5 |
C12—C13—H13 | 120.4 | HB—B1—HC | 109.5 |
| | | |
O3—C3—C4—O4 | 40.0 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O5i | 0.98 | 2.37 | 3.314 (6) | 162 |
C6—H6A···O2ii | 0.97 | 2.43 | 3.352 (6) | 159 |
C18—H18···C9iii | 0.93 | 2.84 | 3.675 (8) | 150 |
C12—H12···O3iv | 0.93 | 2.71 | 3.510 (6) | 145 |
Symmetry codes: (i) −x+1, y+1/2, −z; (ii) −x+1, y−1/2, −z; (iii) x+1, y, z+1; (iv) −x, y−1/2, −z. |
Experimental details
Crystal data |
Chemical formula | C27H32BO6P |
Mr | 494.32 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 293 |
a, b, c (Å) | 10.7567 (19), 9.800 (9), 12.926 (4) |
β (°) | 96.63 (2) |
V (Å3) | 1353.6 (13) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.14 |
Crystal size (mm) | 0.55 × 0.25 × 0.10 |
|
Data collection |
Diffractometer | Enraf-Nonius CAD-4 diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5762, 3105, 1621 |
Rint | 0.142 |
(sin θ/λ)max (Å−1) | 0.639 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.048, 0.144, 1.04 |
No. of reflections | 3105 |
No. of parameters | 319 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.26, −0.22 |
Absolute structure | (Flack, 1983) |
Absolute structure parameter | 0.0 (4) |
Selected geometric parameters (Å, º) topC22—P1 | 1.790 (5) | O4—P1 | 1.600 (3) |
O3—P1 | 1.597 (3) | P1—B1 | 1.851 (6) |
| | | |
C3—O3—P1 | 110.4 (2) | O4—P1—C22 | 105.1 (2) |
C4—O4—P1 | 108.1 (2) | O3—P1—B1 | 115.2 (3) |
O3—P1—O4 | 97.59 (14) | O4—P1—B1 | 115.4 (2) |
O3—P1—C22 | 107.5 (2) | C22—P1—B1 | 114.3 (3) |
| | | |
O3—C3—C4—O4 | 40.0 (2) | | |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O5i | 0.98 | 2.37 | 3.314 (6) | 162 |
C6—H6A···O2ii | 0.97 | 2.43 | 3.352 (6) | 159 |
C18—H18···C9iii | 0.93 | 2.84 | 3.675 (8) | 150 |
C12—H12···O3iv | 0.93 | 2.71 | 3.510 (6) | 145 |
Symmetry codes: (i) −x+1, y+1/2, −z; (ii) −x+1, y−1/2, −z; (iii) x+1, y, z+1; (iv) −x, y−1/2, −z. |
In the drive to design and optimize ligands for asymmetric catalysis, the preparation and characterization of new optically active phosphorus compounds is essential. A great variety of phosphonites have been prepared (Jugé Stephan Genet et al., 1990; Murillo et al., 198?; Reetz et al., 1999), but only a few have been prepared as the corresponding borane complex. The use of a stabilizing complex with borane was developed by Imamoto and co-workers (Imamoto et al., 1987). Borane prevents the phosphinite from oxidizing to the corresponding phosphonate. To our knowledge, no crystal structure of a carbohydrate-derived dioxophospholaneborane complex has been reported prior to the present work.
Electron-deficient P-chiral ligands are rare. Jugé and co-workers have shown the great potential of such compounds, both as ligands and as chiral building blocks in the synthesis of new P-chiral compounds (Jugé Stephan Laffitte & Genet, 1990). Most likely, selective opening of the dioxophospholane borane complex with either lithium or Grignard reagents can give rise to novel carbohydrate-derived phosphonites and ultimately P-chiral phosphines. The title compound, (I), has, in addition to P-chirality, a chiral carbohydrate moiety. The use of a carbohydrate as a chiral auxiliary is very interesting, and the greater peripheral chirality on the carbohydrate moiety induces a highly chiral environment. P-chirality moves a stereocentre closer to a potential metal, a feature that might prove interesting in metal-catalysed reactions. These factors will be explored further in a range of asymmetric reactions. The two Jugé et al. (1990) refs were not distinguished in the original CIF - please check they are correctly cited above and below. \sch
A view of the asymmetric unit of (I), comprising a single molecule, is shown in Fig. 1. The geometries of the five-membered dioxophospholane ring (P1/O10/C10/C11/O11) Should this be P1/O3/C3/C4/O4? and at the P atom are consistent with a similar structure reported earlier (Jugé, 1990). The carbohydrate moiety is in a distorted chair conformation. In the dioxophenylphospolane-borane moiety, the O3—C3—C4—O4 torsion angle is 40.0 (2)°, compared with a value of 60.8 (4)° in the corresponding carbohydrate which is only protected in the anomeric position (Banerjee et al., 1994), and a similar value of 36.63 (2)° in another β-D-galactopyranoside where a five-membered ring is assembled between the 3- and 4-position O atoms (Hoogendorp et al., 1983).
The packing in (I) is governed by non-classical hydrogen-bonding interactions. These can be divided into C—H···π and C—H···O(ethereal type) weak interactions (Table 2). As shown in Fig. 2, the C—H···π interaction results in chains running along the [101] direction. These chains are connected by weak C—H···O interactions (C···O ≈ 3.33 Å) between screw-axis-related molecules (Fig. 3). Finally, a C12—H12···O3 interaction forms a link between the chains, creating a three-dimensional network (Fig. 4a and b).
Table 2. Intermolecular contact geometry (Å, °)