organic compounds
(3aS,4S,6S,7aR)-Hexahydro-3a,5,5-trimethyl-2-phenyl-4,6-methano-1,3,2-benzodioxaborole
aDepartment of Chemistry, Faculty of Science and Technology, University of Tromsø, N-9037 Tromsø, Norway, and bX-ray Structural Centre, A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Street B-334, Moscow 119991, Russian Federation
*Correspondence e-mail: tore.lejon@uit.no
The molecule of the title compound, C16H21BO2, comprises a chiral fused tricyclic system containing five-membered (1,3,2-dioxaborolane), six-membered (cyclohexane) and four-membered (cyclobutane) rings. The 1,3,2-dioxaborolane ring is almost planar (r.m.s. deviation = 0.035 Å), and the syn H and Me substituents at this ring are in an eclipsed conformation. The cyclohexane and cyclobutane rings adopt sofa and butterfly conformations, respectively. The B atom has a trigonal–planar configuration (sum of the bond angles = 360.0°). The phenyl ring is practically coplanar with the 1,3,2-dioxaborolane ring [dihedral angle between the ring planes = 1.96 (8)°]. The was determined from the known configuration of (+)-pinanediol which was used in the synthesis. In the crystal, weak C—H⋯π(Ph) interactions occur.
Related literature
For the Matteson homologation reaction, see: Matteson et al. (1983); Matteson (1989). For 2-substituted (+)-pinanediolboronates, see: Carmès et al. (2000); Caselli et al. (2003); Morandi et al. (2003, 2005).
Experimental
Crystal data
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Refinement
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Data collection: APEX2 (Bruker, 2005); cell SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.
Supporting information
10.1107/S1600536812041712/fb2267sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812041712/fb2267Isup2.hkl
(+)-Pinanediol (10 g, 0.059 mol) was added to a solution of phenylboronic acid (7.16 g, 0.059 mol) in ether (80 ml). The reaction mixture was stirred for 4 h at room temperature. Then the solvent was evaporated under reduced pressure to give the title compound as colourless prismatic crystals. Yield is 15 g (99%). 1H NMR (400 MHz, CDCl3): δ = 8.25 (dd, J = 8.0, 1.4 Hz, 1H), 7.83–7.80 (m, 1H), 7.63–7.35 (m, 3H), 4.46 (dd, J = 8.8, 1.9 Hz, 1H), 2.41 (ddd, J = 8.6, 8.0, 5.6 Hz,1H), 2.23 (ddd, J = 10.8, 6.1, 2.3 Hz, 1H), 2.15 (d, J = 5.9 Hz, 1H), 1.96 (ddd, J = 12.2, 5.5, 3.0 Hz, 2H), 1.49 (s, 3H), 1.32 (s, 3H), 1.23 (d, J = 10.8 Hz, 1H), 0.90 (s, 3H). 13C NMR (101 MHz, CDCl3): δ = 135.62, 134.76, 132.68, 131.15, 127.97, 127.72, 86.22, 78.24, 51.42, 39.54, 38.19, 35.57, 28.71, 27.10, 26.49, 24.04.
All the H atoms were discernible in the difference
Nevertheless, all the H atoms were fully constrained. The values of the used constraints were following: Caryl—H = 0.95, Cmethyl—H = 0.98, Cmethylene—H = 0.99, Cmethine—H = 1.00 Å; Uiso(H) = 1.2Ueq(Caryl/methylene/methine); Uiso(H) = 1.5Ueq(Cmethyl). After the converged the extremal residual density peaks equalled to -0.197 and 0.302 e A-3. All the highest positive peaks in the range of 0.170–0.302 e A-3) were situated between the covalently bonded atoms. 2225 Friedel pairs were merged in the process. The was determined from the known configuration of (+)-pinanediol that had been used in the synthesis.Data collection: APEX2 (Bruker, 2005); cell
SAINT-Plus (Bruker, 2001); data reduction: SAINT-Plus (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).C16H21BO2 | F(000) = 552 |
Mr = 256.14 | Dx = 1.210 Mg m−3 |
Orthorhombic, P212121 | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: P 2ac 2ab | Cell parameters from 7519 reflections |
a = 8.4974 (3) Å | θ = 2.3–32.2° |
b = 11.8566 (4) Å | µ = 0.08 mm−1 |
c = 13.9580 (4) Å | T = 100 K |
V = 1406.27 (8) Å3 | Prism, colourless |
Z = 4 | 0.25 × 0.22 × 0.18 mm |
Bruker APEXII CCD diffractometer | 2905 independent reflections |
Radiation source: fine-focus sealed tube | 2717 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
ϕ and ω scans | θmax = 32.7°, θmin = 2.3° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | h = −12→12 |
Tmin = 0.981, Tmax = 0.986 | k = −17→18 |
21778 measured reflections | l = −21→21 |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.034 | H-atom parameters constrained |
wR(F2) = 0.092 | w = 1/[σ2(Fo2) + (0.0609P)2 + 0.0967P] where P = (Fo2 + 2Fc2)/3 |
S = 1.05 | (Δ/σ)max < 0.001 |
2905 reflections | Δρmax = 0.30 e Å−3 |
176 parameters | Δρmin = −0.20 e Å−3 |
0 restraints | Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.015 (3) |
C16H21BO2 | V = 1406.27 (8) Å3 |
Mr = 256.14 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 8.4974 (3) Å | µ = 0.08 mm−1 |
b = 11.8566 (4) Å | T = 100 K |
c = 13.9580 (4) Å | 0.25 × 0.22 × 0.18 mm |
Bruker APEXII CCD diffractometer | 2905 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 2717 reflections with I > 2σ(I) |
Tmin = 0.981, Tmax = 0.986 | Rint = 0.037 |
21778 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.092 | H-atom parameters constrained |
S = 1.05 | Δρmax = 0.30 e Å−3 |
2905 reflections | Δρmin = −0.20 e Å−3 |
176 parameters |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. |
Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.47304 (10) | 0.46977 (7) | 0.16126 (6) | 0.01697 (16) | |
B2 | 0.51357 (15) | 0.50773 (11) | 0.07183 (9) | 0.0155 (2) | |
O3 | 0.43471 (10) | 0.60223 (7) | 0.04344 (6) | 0.01612 (16) | |
C3A | 0.33535 (12) | 0.64035 (9) | 0.12251 (7) | 0.01379 (18) | |
C4 | 0.16707 (12) | 0.65105 (9) | 0.08556 (7) | 0.01398 (18) | |
H4 | 0.1503 | 0.7117 | 0.0368 | 0.017* | |
C5 | 0.04178 (12) | 0.64743 (9) | 0.16843 (8) | 0.01482 (18) | |
C6 | 0.05741 (14) | 0.51655 (9) | 0.16181 (8) | 0.0170 (2) | |
H6 | −0.0424 | 0.4734 | 0.1719 | 0.020* | |
C7 | 0.19909 (14) | 0.47449 (10) | 0.21897 (8) | 0.0181 (2) | |
H7A | 0.2184 | 0.3944 | 0.2029 | 0.022* | |
H7B | 0.1743 | 0.4788 | 0.2882 | 0.022* | |
C7A | 0.35083 (13) | 0.54313 (9) | 0.19900 (7) | 0.01454 (19) | |
H7C | 0.3886 | 0.5765 | 0.2606 | 0.017* | |
C8 | 0.10773 (14) | 0.53195 (10) | 0.05572 (8) | 0.0182 (2) | |
H8A | 0.0190 | 0.5329 | 0.0097 | 0.022* | |
H8B | 0.1920 | 0.4800 | 0.0346 | 0.022* | |
C9 | 0.40689 (14) | 0.75145 (9) | 0.15593 (8) | 0.0180 (2) | |
H9A | 0.4052 | 0.8059 | 0.1031 | 0.027* | |
H9B | 0.5158 | 0.7388 | 0.1763 | 0.027* | |
H9C | 0.3457 | 0.7811 | 0.2098 | 0.027* | |
C10 | −0.11904 (13) | 0.68839 (11) | 0.13230 (9) | 0.0195 (2) | |
H10A | −0.1992 | 0.6736 | 0.1812 | 0.029* | |
H10B | −0.1464 | 0.6482 | 0.0733 | 0.029* | |
H10C | −0.1142 | 0.7696 | 0.1194 | 0.029* | |
C11 | 0.07336 (14) | 0.70381 (10) | 0.26519 (8) | 0.0189 (2) | |
H11A | −0.0121 | 0.6856 | 0.3097 | 0.028* | |
H11B | 0.0791 | 0.7857 | 0.2566 | 0.028* | |
H11C | 0.1733 | 0.6762 | 0.2912 | 0.028* | |
C12 | 0.63777 (13) | 0.44754 (9) | 0.00804 (8) | 0.01522 (19) | |
C13 | 0.68207 (13) | 0.49218 (10) | −0.08098 (8) | 0.0167 (2) | |
H13 | 0.6353 | 0.5602 | −0.1029 | 0.020* | |
C14 | 0.79409 (15) | 0.43795 (10) | −0.13785 (8) | 0.0191 (2) | |
H14 | 0.8243 | 0.4695 | −0.1976 | 0.023* | |
C15 | 0.86127 (14) | 0.33749 (10) | −0.10656 (9) | 0.0202 (2) | |
H15 | 0.9356 | 0.2995 | −0.1459 | 0.024* | |
C16 | 0.82009 (15) | 0.29237 (10) | −0.01792 (9) | 0.0219 (2) | |
H16 | 0.8673 | 0.2243 | 0.0037 | 0.026* | |
C17 | 0.70942 (14) | 0.34746 (10) | 0.03884 (8) | 0.0186 (2) | |
H17 | 0.6820 | 0.3167 | 0.0994 | 0.022* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0158 (4) | 0.0176 (4) | 0.0175 (3) | 0.0048 (3) | 0.0017 (3) | 0.0028 (3) |
B2 | 0.0141 (5) | 0.0152 (5) | 0.0171 (5) | 0.0012 (4) | 0.0001 (4) | −0.0003 (4) |
O3 | 0.0159 (4) | 0.0166 (3) | 0.0159 (3) | 0.0034 (3) | 0.0031 (3) | 0.0019 (3) |
C3A | 0.0135 (4) | 0.0135 (4) | 0.0144 (4) | 0.0010 (4) | 0.0011 (3) | 0.0007 (3) |
C4 | 0.0129 (4) | 0.0138 (4) | 0.0152 (4) | −0.0002 (3) | 0.0001 (3) | 0.0006 (3) |
C5 | 0.0127 (4) | 0.0146 (4) | 0.0172 (4) | −0.0005 (4) | 0.0003 (4) | −0.0001 (4) |
C6 | 0.0153 (4) | 0.0139 (4) | 0.0217 (5) | −0.0018 (4) | −0.0006 (4) | 0.0010 (4) |
C7 | 0.0167 (5) | 0.0157 (4) | 0.0218 (5) | −0.0006 (4) | 0.0016 (4) | 0.0047 (4) |
C7A | 0.0140 (4) | 0.0145 (4) | 0.0151 (4) | 0.0020 (4) | 0.0010 (3) | 0.0008 (4) |
C8 | 0.0187 (5) | 0.0169 (5) | 0.0191 (5) | −0.0017 (4) | −0.0019 (4) | −0.0036 (4) |
C9 | 0.0157 (5) | 0.0151 (4) | 0.0231 (5) | −0.0019 (4) | 0.0004 (4) | −0.0004 (4) |
C10 | 0.0143 (5) | 0.0214 (5) | 0.0228 (5) | 0.0020 (4) | −0.0003 (4) | 0.0026 (4) |
C11 | 0.0182 (5) | 0.0203 (5) | 0.0182 (5) | 0.0007 (4) | 0.0022 (4) | −0.0024 (4) |
C12 | 0.0138 (4) | 0.0151 (4) | 0.0167 (4) | −0.0001 (4) | −0.0001 (4) | −0.0014 (4) |
C13 | 0.0158 (5) | 0.0170 (5) | 0.0173 (4) | 0.0002 (4) | −0.0008 (4) | −0.0004 (4) |
C14 | 0.0191 (5) | 0.0213 (5) | 0.0169 (5) | −0.0010 (4) | 0.0014 (4) | −0.0021 (4) |
C15 | 0.0179 (5) | 0.0207 (5) | 0.0220 (5) | 0.0013 (4) | 0.0040 (4) | −0.0043 (4) |
C16 | 0.0205 (5) | 0.0180 (5) | 0.0272 (5) | 0.0054 (4) | 0.0036 (4) | 0.0004 (4) |
C17 | 0.0175 (5) | 0.0180 (5) | 0.0204 (5) | 0.0031 (4) | 0.0034 (4) | 0.0015 (4) |
O1—B2 | 1.3709 (15) | C8—H8B | 0.9900 |
O1—C7A | 1.4535 (13) | C9—H9A | 0.9800 |
B2—O3 | 1.3644 (15) | C9—H9B | 0.9800 |
B2—C12 | 1.5544 (16) | C9—H9C | 0.9800 |
O3—C3A | 1.4612 (13) | C10—H10A | 0.9800 |
C3A—C9 | 1.5239 (15) | C10—H10B | 0.9800 |
C3A—C4 | 1.5254 (15) | C10—H10C | 0.9800 |
C3A—C7A | 1.5767 (15) | C11—H11A | 0.9800 |
C4—C8 | 1.5563 (16) | C11—H11B | 0.9800 |
C4—C5 | 1.5727 (15) | C11—H11C | 0.9800 |
C4—H4 | 1.0000 | C12—C17 | 1.4012 (15) |
C5—C11 | 1.5307 (15) | C12—C13 | 1.4020 (15) |
C5—C10 | 1.5355 (15) | C13—C14 | 1.3963 (16) |
C5—C6 | 1.5602 (15) | C13—H13 | 0.9500 |
C6—C7 | 1.5280 (16) | C14—C15 | 1.3911 (17) |
C6—C8 | 1.5520 (17) | C14—H14 | 0.9500 |
C6—H6 | 1.0000 | C15—C16 | 1.3927 (17) |
C7—C7A | 1.5500 (16) | C15—H15 | 0.9500 |
C7—H7A | 0.9900 | C16—C17 | 1.3924 (16) |
C7—H7B | 0.9900 | C16—H16 | 0.9500 |
C7A—H7C | 1.0000 | C17—H17 | 0.9500 |
C8—H8A | 0.9900 | ||
B2—O1—C7A | 108.24 (9) | C6—C8—H8A | 114.2 |
O3—B2—O1 | 114.25 (10) | C4—C8—H8A | 114.2 |
O3—B2—C12 | 122.96 (10) | C6—C8—H8B | 114.2 |
O1—B2—C12 | 122.78 (10) | C4—C8—H8B | 114.2 |
B2—O3—C3A | 108.56 (8) | H8A—C8—H8B | 111.4 |
O3—C3A—C9 | 105.55 (8) | C3A—C9—H9A | 109.5 |
O3—C3A—C4 | 108.18 (8) | C3A—C9—H9B | 109.5 |
C9—C3A—C4 | 113.93 (9) | H9A—C9—H9B | 109.5 |
O3—C3A—C7A | 103.72 (8) | C3A—C9—H9C | 109.5 |
C9—C3A—C7A | 113.04 (9) | H9A—C9—H9C | 109.5 |
C4—C3A—C7A | 111.59 (9) | H9B—C9—H9C | 109.5 |
C3A—C4—C8 | 108.59 (9) | C5—C10—H10A | 109.5 |
C3A—C4—C5 | 112.56 (8) | C5—C10—H10B | 109.5 |
C8—C4—C5 | 87.29 (8) | H10A—C10—H10B | 109.5 |
C3A—C4—H4 | 115.1 | C5—C10—H10C | 109.5 |
C8—C4—H4 | 115.1 | H10A—C10—H10C | 109.5 |
C5—C4—H4 | 115.1 | H10B—C10—H10C | 109.5 |
C11—C5—C10 | 107.92 (9) | C5—C11—H11A | 109.5 |
C11—C5—C6 | 118.15 (9) | C5—C11—H11B | 109.5 |
C10—C5—C6 | 111.77 (9) | H11A—C11—H11B | 109.5 |
C11—C5—C4 | 121.22 (9) | C5—C11—H11C | 109.5 |
C10—C5—C4 | 110.62 (9) | H11A—C11—H11C | 109.5 |
C6—C5—C4 | 85.75 (8) | H11B—C11—H11C | 109.5 |
C7—C6—C8 | 108.63 (10) | C17—C12—C13 | 118.35 (10) |
C7—C6—C5 | 111.14 (9) | C17—C12—B2 | 120.53 (10) |
C8—C6—C5 | 87.88 (8) | C13—C12—B2 | 121.11 (10) |
C7—C6—H6 | 115.3 | C14—C13—C12 | 120.87 (11) |
C8—C6—H6 | 115.3 | C14—C13—H13 | 119.6 |
C5—C6—H6 | 115.3 | C12—C13—H13 | 119.6 |
C6—C7—C7A | 112.97 (9) | C15—C14—C13 | 119.71 (11) |
C6—C7—H7A | 109.0 | C15—C14—H14 | 120.1 |
C7A—C7—H7A | 109.0 | C13—C14—H14 | 120.1 |
C6—C7—H7B | 109.0 | C14—C15—C16 | 120.31 (11) |
C7A—C7—H7B | 109.0 | C14—C15—H15 | 119.8 |
H7A—C7—H7B | 107.8 | C16—C15—H15 | 119.8 |
O1—C7A—C7 | 110.20 (9) | C17—C16—C15 | 119.67 (11) |
O1—C7A—C3A | 104.58 (8) | C17—C16—H16 | 120.2 |
C7—C7A—C3A | 115.87 (9) | C15—C16—H16 | 120.2 |
O1—C7A—H7C | 108.7 | C16—C17—C12 | 121.07 (11) |
C7—C7A—H7C | 108.7 | C16—C17—H17 | 119.5 |
C3A—C7A—H7C | 108.7 | C12—C17—H17 | 119.5 |
C6—C8—C4 | 86.60 (8) | ||
C7A—O1—B2—O3 | 1.42 (13) | B2—O1—C7A—C7 | 119.37 (10) |
C7A—O1—B2—C12 | −178.09 (10) | B2—O1—C7A—C3A | −5.80 (11) |
O1—B2—O3—C3A | 4.09 (13) | C6—C7—C7A—O1 | −120.17 (10) |
C12—B2—O3—C3A | −176.40 (10) | C6—C7—C7A—C3A | −1.72 (14) |
B2—O3—C3A—C9 | 111.83 (10) | O3—C3A—C7A—O1 | 7.86 (10) |
B2—O3—C3A—C4 | −125.86 (10) | C9—C3A—C7A—O1 | −105.95 (10) |
B2—O3—C3A—C7A | −7.25 (11) | C4—C3A—C7A—O1 | 124.09 (9) |
O3—C3A—C4—C8 | 63.98 (10) | O3—C3A—C7A—C7 | −113.64 (10) |
C9—C3A—C4—C8 | −178.99 (9) | C9—C3A—C7A—C7 | 132.54 (10) |
C7A—C3A—C4—C8 | −49.50 (11) | C4—C3A—C7A—C7 | 2.59 (13) |
O3—C3A—C4—C5 | 158.89 (8) | C7—C6—C8—C4 | −85.15 (9) |
C9—C3A—C4—C5 | −84.08 (11) | C5—C6—C8—C4 | 26.47 (8) |
C7A—C3A—C4—C5 | 45.42 (12) | C3A—C4—C8—C6 | 86.66 (9) |
C3A—C4—C5—C11 | 37.66 (14) | C5—C4—C8—C6 | −26.25 (8) |
C8—C4—C5—C11 | 146.68 (10) | O3—B2—C12—C17 | −176.74 (11) |
C3A—C4—C5—C10 | 165.43 (9) | O1—B2—C12—C17 | 2.72 (17) |
C8—C4—C5—C10 | −85.55 (10) | O3—B2—C12—C13 | 3.88 (17) |
C3A—C4—C5—C6 | −82.88 (10) | O1—B2—C12—C13 | −176.66 (11) |
C8—C4—C5—C6 | 26.13 (8) | C17—C12—C13—C14 | 0.39 (17) |
C11—C5—C6—C7 | −40.37 (13) | B2—C12—C13—C14 | 179.78 (11) |
C10—C5—C6—C7 | −166.49 (9) | C12—C13—C14—C15 | 0.88 (17) |
C4—C5—C6—C7 | 82.98 (10) | C13—C14—C15—C16 | −1.55 (18) |
C11—C5—C6—C8 | −149.55 (10) | C14—C15—C16—C17 | 0.94 (19) |
C10—C5—C6—C8 | 84.33 (10) | C15—C16—C17—C12 | 0.36 (19) |
C4—C5—C6—C8 | −26.20 (8) | C13—C12—C17—C16 | −1.01 (17) |
C8—C6—C7—C7A | 47.70 (12) | B2—C12—C17—C16 | 179.59 (11) |
C5—C6—C7—C7A | −47.38 (13) |
Cg is the centroid of the C12–C17 phenyl ring |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8A···Cgi | 0.99 | 2.94 | 3.7532 (13) | 140 |
C11—H11A···Cgii | 0.98 | 2.97 | 3.9481 (13) | 174 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1/2, −y+1, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C16H21BO2 |
Mr | 256.14 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 100 |
a, b, c (Å) | 8.4974 (3), 11.8566 (4), 13.9580 (4) |
V (Å3) | 1406.27 (8) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.25 × 0.22 × 0.18 |
Data collection | |
Diffractometer | Bruker APEXII CCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.981, 0.986 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 21778, 2905, 2717 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.759 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.092, 1.05 |
No. of reflections | 2905 |
No. of parameters | 176 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.30, −0.20 |
Computer programs: APEX2 (Bruker, 2005), SAINT-Plus (Bruker, 2001), SHELXTL (Sheldrick, 2008).
Cg is the centroid of the C12–C17 phenyl ring |
D—H···A | D—H | H···A | D···A | D—H···A |
C8—H8A···Cgi | 0.99 | 2.94 | 3.7532 (13) | 140 |
C11—H11A···Cgii | 0.98 | 2.97 | 3.9481 (13) | 174 |
Symmetry codes: (i) x−1, y, z; (ii) −x+1/2, −y+1, z+1/2. |
Acknowledgements
The Norwegian Research Council is acknowledged for research grant 166742.
References
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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.
2-Substituted (+)-pinanediolboronates are well known compounds (Carmès et al., 2000; Caselli et al., 2003; Morandi et al., 2003; Morandi et al., 2005). In the present work, the (+)-pinanediol phenylboronate (CAS Registry Number: 76110-78-6) has been synthesized by the reaction of phenylboronic acid with (+)-pinanediol in diethyl ether (Fig. 1) as a starting material for the Matteson homologation reaction (Matteson et al., 1983; Matteson, 1989).
The molecule of the title compound, C16H21BO2, comprises a chiral fused tricyclic system containing five-membered (1,3,2-dioxaborolane), six-membered (cyclohexane) and four-membered (cyclobutane) rings (Fig. 2). The 1,3,2-dioxaborolane ring is almost planar (s.u. = 0.035 Å), and syn hydrogen and methyl substituents at this ring are in an eclipsed conformation. The cyclohexane (C8/C4/C3a/C7a/C7/C6 and C5/C4/C3a/C7a/C7/C6) and cyclobutane rings adopt sofa and butterfly conformations, respectively. The boron atom has a trigonal-planar configuration (sum of the bond angles is 360.0 (3)°). The phenyl ring is practically coplanar to the 1,3,2-dioxaborolane ring (the interplanar angle between the ring planes is 1.96 (8)°).
The absolute structure was determined from the known configuration of (+)-pinanediol that has been used in the synthesis. The title molecule possesses four asymmetric centres at C3a, C4, C6 and C7a carbon atoms. The configurations at these asymmetric centres are S, S, S, R, respectively.
The crystal packing of the title molecules is stabilized by the weak intermolecular C8—H8A···π(Ph) [the H···Cgi distance is 2.94 Å; Cg means the centroid of the phenyl ring composed of C12/C13–C17] and C11—H11A···π(Ph) [the H···Cgii distance is 2.97 Å] interactions. Symmetry codes: (i) -1 + x, y, z; (ii) 1/2 - x, 1 - y, 1/2 + z.