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The structures of three chiral vinyldioxaza­borocanes are reported, namely (2E)- and (2Z)-6-benzyl-2-buten-2-yl-1,3,6,2-dioxaza­borocane, C27H30BNO2, (II) and (III), respectively, and (2Z)-2-buten-2-yl-6-isobutyl-1,3,6,2-dioxaza­boro­cane, C24H32BNO2, (IV). These compounds may be useful in asymmetric reactions. In the structures reported here, the N-B donor-acceptor bond is longer than in any previously reported analogous compounds.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270106013527/rb3006sup1.cif
Contains datablocks II, III, IV, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106013527/rb3006IIsup2.hkl
Contains datablock mn1716

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106013527/rb3006IIIsup3.hkl
Contains datablock mn1718z

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270106013527/rb3006IVsup4.hkl
Contains datablock jf1206

CCDC references: 612454; 612455; 612456

Comment top

Enantiomerically pure organoboron compounds are versatile synthetic intermediates that can be transformed into numerous functionalities without loss of optical purity (Brown & Singaram, 1987, 1988). Different methods for their synthesis therefore continue to be developed. Vinyl boronates containing a chiral auxiliary via attachment to the boron group are potentially useful starting materials for the production of these compounds. Such vinyl boronates have been used to control the absolute stereochemistry of cyclopropanations (Imai et al., 1990; Pietruszka & Widenmayer, 1997), Diels–Alder reactions (Bonk & Avery, 1997) and dipolar cycloadditions (Marsden et al., 1998, 2000). We recently reported a novel method for the synthesis of chiral organoboron compounds via asymmetric hydrogenation of vinyl oxazaborolidines under ambient conditions (Gamsey et al., 2005). However, although relatively easy to prepare, these chiral vinyl oxazaborolidines have a few drawbacks in terms of their utility in asymmetric reactions. For example, apart from being hydrolytically unstable, the prochiral olefin is somewhat distal from the chiral ligand, due to the planarity of the boronate group. We anticipated that both these problems could be ameliorated through the use of vinyl dioxazaborocanes. Since dioxazaborocanes are stable to air and water, their preparation, isolation, storage and handling are straightforward. Most importantly, the tetrahedral geometry of the B atom should exert more sterochemical influence in asymmetric reactions (Seebach et al., 1996). Marsden et al. (2000) have synthesized vinyl dioxazaborocanes from trans-disubstituted alkenylboronic acids. We report here the synthesis and X-ray structures of three new vinyl dioxazaborocanes, (II)–(IV), derived from α-substituted alkenylboronic acids. Diolamines (Ia) and (Ib) were synthesized from either benzylamine or isobutylamine and two equivalents of (R)-(+)-styrene oxide, according to previously published procedures (Trost et al., 1992; Sundararajan & Manickam, 1997).

The compounds in this report were synthesized as shown in the scheme. The structural results confirm that they are chiral. Compounds (II), (III) and (IV) all crystallize with no molecules of solvation and no unusual intermolecular contacts. Their structures are depicted in Figs. 1, 2 and 3, respectively. Compound (IV) has two molecules in the asymmetric unit which differ slightly in the dihedral angles of the phenyl rings. In addition, the two N—B distances differ by five s.u.s for no apparent reason.

In all three compounds, each of the dioxazaborocane rings is in a chair-like conformation. The most surprising structural feature is the length of the N—B donor–acceptor bonds, which are significantly longer than those in the previously reported structures with the same dioxazaborocane ring size and similar derivatization (Rettig & Trotter, 1975; Caron & Hawkins, 1998; Doidge-Harrison et al., 1998; Thadani et al., 2001a,b, 2002; Sopková-de Oliveira Santos et al., 2004). In this set of eight related molecules, the average N—B bond length is 1.667[11] Å, whereas it is 1.778[8] Å in the four independent molecules in this study (the average deviations from the mean are given in square brackets).

The individual bond distances involving N and B are presented in Tables 1–3 for compounds (II), (III) and (IV), respectively. In seven of the previous structures, the N atom is bonded to H, and in the eighth it is bonded to methyl. It has already been noted (Sopková-de Oliveira Santos et al., 2004) that the N—B bond is lengthened [1.696 (7) Å] in the methyl derivative. However, the lengthening is far greater in (II), (III) and (IV), in which the N atom is bonded to either benzyl or iBu groups. Thus, the bulkier substituent appears to have an impact on the basicity of the N atom. In fact, an examination of the degree of pyramidalization of both the N and B atoms in this study shows that they are flattened relative to the other eight similar molecules. Using the program POAV1 (Haddon, 1999), the pyramidalization angles at N and B in this study have averages of 16.4 and 13.6°, respectively (the angle for sp2 is 0° and for sp3 is 19.5°). Average values for the other eight structures are 17.4 and 15.6° for N and B, respectively. These results suggest a loss of p character in the lone-pair orbital used by N and a weaker dative bond, in agreement with the increased bond length.

Experimental top

For the preparation of each of compounds (II)–(IV), boronic acid (2.7 mmol) was added to a solution of the diolamine [Which diolamine for which compound?] (2.8 mmol) in dry [Diethyl?] ether (10 ml). CaH2 (6 mmol) was added and the reaction was refluxed for 12 h. The CaH2 was filtered off and the ether was removed under reduced pressure, affording the dioxazaborocanes as white foams. Single crystals of compounds (II) and (IV) for X-ray analysis were obtained by dissolving the compounds in a minimal amount of warm diethyl ether and allowing the flask to stand at room temperature overnight. Single crystals of compound (III) for X-ray analysis were obtained similarly, but CDCl3–diethyl ether (1:1) was used as the recrystallization solvent.

Refinement top

For (II) and (III), H atoms were treated as riding, with fixed C—H distances in the range 0.95–1.00 Å, and with Uiso(H) = 1.2Ueq(C). For (IV), H atoms were freely refined with the use of isotropic displacement parameters, yielding a range of C—H distances of 0.93 (3)–1.03 (3) Å. Friedel pairs were merged for the final refinement in all three structures. The absolute configurations of all three compounds were assumed from the synthesis.

Computing details top

Data collection: APEX2 (Bruker, 2004) for (II), (III); SMART (Bruker, 2003) for (IV). Cell refinement: SAINT (Bruker, 2004) for (II), (III); SAINT (Bruker, 2003) for (IV). Data reduction: SAINT (Bruker, 2004) for (II), (III); SAINT (Bruker, 2003) for (IV). For all compounds, program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP in SHELXTL (Sheldrick, 1994); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. A drawing of the structure of (II), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 2] Fig. 2. A drawing of the structure of (III), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.
[Figure 3] Fig. 3. A drawing of the structure of (IV), showing the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii. Only one of the two molecules is shown; the second molecule shows no distinctive differences in overall geometry.
(II) (2Z)-6-benzyl-2-buten-2-yl-1,3,6,2-dioxazaborocane top
Crystal data top
C27H30BNO2F(000) = 880
Mr = 411.33Dx = 1.175 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 9196 reflections
a = 12.0141 (4) Åθ = 2.4–30.2°
b = 12.3388 (5) ŵ = 0.07 mm1
c = 15.6913 (6) ÅT = 90 K
V = 2326.07 (15) Å3Needle, colourless
Z = 40.40 × 0.04 × 0.03 mm
Data collection top
Bruker SMART APEXII
diffractometer
3885 independent reflections
Radiation source: fine-focus sealed tube3493 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.030
Detector resolution: 8.3 pixels mm-1θmax = 30.3°, θmin = 2.1°
ω scansh = 1717
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
k = 1717
Tmin = 0.990, Tmax = 0.998l = 2222
32109 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.037Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H-atom parameters constrained
S = 1.03 w = 1/[σ2(Fo2) + (0.0633P)2 + 0.2206P]
where P = (Fo2 + 2Fc2)/3
3885 reflections(Δ/σ)max < 0.001
282 parametersΔρmax = 0.26 e Å3
0 restraintsΔρmin = 0.16 e Å3
Crystal data top
C27H30BNO2V = 2326.07 (15) Å3
Mr = 411.33Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 12.0141 (4) ŵ = 0.07 mm1
b = 12.3388 (5) ÅT = 90 K
c = 15.6913 (6) Å0.40 × 0.04 × 0.03 mm
Data collection top
Bruker SMART APEXII
diffractometer
3885 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
3493 reflections with I > 2σ(I)
Tmin = 0.990, Tmax = 0.998Rint = 0.030
32109 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0370 restraints
wR(F2) = 0.099H-atom parameters constrained
S = 1.03Δρmax = 0.26 e Å3
3885 reflectionsΔρmin = 0.16 e Å3
282 parameters
Special details top

Experimental. Compound II: 97% yield. [α]D25 = 35.0° (c = 4.3, CHCl3); 1H NMR (500 MHz, CCDl3): δ 1.80 (d, J= 7 Hz, 3H), 1.93 (s, 3H), 2.53 (t, J = 11.5 Hz, 1H), 2.72 (t, J = 10.75 Hz, 1H), 2.94 (dd, J = 11, 3.5 Hz, 1H), 3.60 (dd, J = 12.5, 4.5 Hz, 1H), 3.88 (d, J = 14 Hz, 1H), 4.07 (d, J = 14.5 Hz, 1H), 5.23 (dd, J = 10.5, 4 Hz, 2H), 6.34 (q, J = 7, Hz, 1H), 7.29–7.39 (m, 10H), 7.53 (t, J = 7.75 Hz, 4H); 13C NMR (125 MHz, CDCl3): δ 14.43, 15.78, 59.80, 60.25, 66.24, 73.39, 73.75, 125.80, 126.14, 127.79, 127.82, 128.58, 129.17, 129.28, 131.10, 131.55, 133.06, 141.09, 141.58; 11B NMR (80.25 MHz, CDCl3): δ 15.29.

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
xyzUiso*/Ueq
O10.56682 (9)0.52069 (9)0.41157 (7)0.0277 (2)
O20.65189 (8)0.45888 (8)0.27993 (7)0.0260 (2)
N10.76852 (9)0.47946 (9)0.40810 (7)0.0226 (2)
C10.59091 (11)0.43605 (12)0.46886 (9)0.0245 (3)
H10.57940.36420.44060.029*
C20.71433 (11)0.45195 (13)0.49076 (9)0.0246 (3)
H2A0.72390.51150.53240.029*
H2B0.74640.38480.51500.029*
C30.79537 (12)0.38110 (12)0.35666 (9)0.0236 (3)
H3A0.75500.31690.37860.028*
H3B0.87630.36600.35760.028*
C40.75664 (12)0.40982 (12)0.26662 (9)0.0236 (3)
H40.80910.46340.24060.028*
C50.52088 (12)0.44382 (13)0.54868 (10)0.0289 (3)
C60.45133 (13)0.53172 (17)0.56272 (11)0.0380 (4)
H60.44460.58700.52090.046*
C70.39109 (14)0.5386 (2)0.63887 (12)0.0491 (5)
H70.34290.59840.64820.059*
C80.40092 (15)0.4594 (2)0.70042 (11)0.0492 (5)
H80.35950.46480.75180.059*
C90.47155 (18)0.37193 (18)0.68713 (12)0.0475 (5)
H90.47900.31760.72960.057*
C100.53137 (18)0.36414 (15)0.61132 (11)0.0413 (4)
H100.57960.30420.60220.050*
C110.86861 (11)0.55095 (12)0.42022 (9)0.0255 (3)
H11A0.84380.62140.44380.031*
H11B0.90270.56510.36390.031*
C120.95611 (12)0.50354 (11)0.47866 (9)0.0242 (3)
C130.94934 (13)0.51939 (13)0.56683 (9)0.0291 (3)
H130.89030.56150.58970.035*
C141.02784 (13)0.47436 (14)0.62123 (10)0.0327 (3)
H141.02110.48440.68100.039*
C151.11570 (14)0.41504 (13)0.58899 (10)0.0309 (3)
H151.16940.38440.62630.037*
C161.12496 (13)0.40044 (13)0.50137 (11)0.0300 (3)
H161.18580.36060.47870.036*
C171.04537 (12)0.44393 (13)0.44684 (9)0.0274 (3)
H171.05200.43280.38710.033*
C180.74702 (12)0.31199 (12)0.20997 (9)0.0240 (3)
C190.83359 (14)0.28520 (14)0.15487 (10)0.0309 (3)
H190.89710.33080.15090.037*
C200.82705 (17)0.19167 (16)0.10555 (10)0.0396 (4)
H200.88690.17270.06890.047*
C210.73421 (17)0.12659 (15)0.10963 (11)0.0417 (4)
H210.73000.06300.07560.050*
C220.64688 (15)0.15353 (15)0.16325 (12)0.0377 (4)
H220.58250.10890.16550.045*
C230.65341 (13)0.24593 (13)0.21375 (10)0.0290 (3)
H230.59380.26390.25090.035*
C240.66847 (12)0.66011 (12)0.32330 (9)0.0248 (3)
C250.68680 (14)0.68679 (13)0.24179 (10)0.0310 (3)
H250.69800.62810.20350.037*
C260.69180 (19)0.79861 (16)0.20332 (13)0.0450 (4)
H26A0.64420.80130.15260.067*
H26B0.76870.81530.18720.067*
H26C0.66570.85190.24510.067*
C270.64758 (15)0.74444 (13)0.39113 (10)0.0334 (3)
H27A0.65990.81680.36720.050*
H27B0.69870.73270.43890.050*
H27C0.57060.73860.41130.050*
B10.65489 (13)0.53563 (13)0.34979 (10)0.0235 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0248 (5)0.0296 (5)0.0287 (5)0.0027 (4)0.0050 (4)0.0070 (4)
O20.0241 (4)0.0253 (5)0.0287 (5)0.0039 (4)0.0036 (4)0.0025 (4)
N10.0232 (5)0.0229 (5)0.0216 (5)0.0017 (4)0.0025 (4)0.0002 (4)
C10.0250 (6)0.0261 (7)0.0224 (6)0.0040 (5)0.0016 (5)0.0026 (5)
C20.0262 (6)0.0268 (7)0.0207 (6)0.0046 (5)0.0016 (5)0.0008 (5)
C30.0242 (6)0.0224 (6)0.0243 (6)0.0025 (5)0.0009 (5)0.0000 (5)
C40.0225 (6)0.0248 (6)0.0235 (6)0.0007 (5)0.0001 (5)0.0016 (5)
C50.0256 (6)0.0358 (7)0.0253 (6)0.0118 (6)0.0031 (5)0.0015 (6)
C60.0252 (7)0.0602 (11)0.0286 (7)0.0025 (7)0.0008 (6)0.0001 (8)
C70.0273 (7)0.0857 (15)0.0341 (8)0.0074 (9)0.0044 (7)0.0069 (10)
C80.0306 (8)0.0911 (16)0.0259 (7)0.0222 (10)0.0067 (6)0.0051 (9)
C90.0578 (11)0.0555 (11)0.0293 (8)0.0257 (10)0.0073 (8)0.0021 (8)
C100.0549 (10)0.0369 (9)0.0320 (8)0.0147 (8)0.0096 (8)0.0020 (7)
C110.0247 (6)0.0232 (6)0.0287 (7)0.0045 (5)0.0006 (5)0.0022 (5)
C120.0235 (6)0.0241 (6)0.0251 (6)0.0060 (5)0.0012 (5)0.0007 (5)
C130.0268 (6)0.0326 (7)0.0278 (7)0.0067 (6)0.0033 (5)0.0095 (6)
C140.0334 (7)0.0423 (9)0.0223 (6)0.0125 (7)0.0003 (6)0.0036 (6)
C150.0310 (7)0.0317 (7)0.0301 (7)0.0069 (6)0.0068 (6)0.0023 (6)
C160.0267 (7)0.0302 (7)0.0330 (7)0.0006 (6)0.0002 (6)0.0025 (6)
C170.0267 (6)0.0320 (7)0.0234 (6)0.0030 (6)0.0020 (5)0.0010 (6)
C180.0254 (6)0.0274 (6)0.0192 (6)0.0054 (5)0.0023 (5)0.0023 (5)
C190.0314 (7)0.0373 (8)0.0241 (7)0.0088 (6)0.0033 (6)0.0072 (6)
C200.0504 (10)0.0476 (9)0.0207 (7)0.0224 (8)0.0027 (7)0.0012 (7)
C210.0557 (11)0.0404 (9)0.0291 (8)0.0170 (8)0.0170 (8)0.0123 (7)
C220.0371 (8)0.0356 (8)0.0403 (9)0.0039 (7)0.0157 (7)0.0086 (7)
C230.0268 (6)0.0313 (7)0.0288 (7)0.0025 (6)0.0033 (6)0.0031 (6)
C240.0258 (6)0.0231 (6)0.0254 (6)0.0005 (5)0.0014 (5)0.0004 (5)
C250.0353 (8)0.0291 (7)0.0286 (7)0.0009 (6)0.0025 (6)0.0040 (6)
C260.0588 (11)0.0384 (9)0.0376 (9)0.0052 (9)0.0026 (8)0.0132 (8)
C270.0421 (8)0.0273 (7)0.0307 (8)0.0019 (7)0.0031 (7)0.0025 (6)
B10.0230 (6)0.0247 (7)0.0227 (7)0.0014 (6)0.0010 (5)0.0022 (6)
Geometric parameters (Å, º) top
O1—C11.4080 (17)C12—C131.400 (2)
O1—B11.4469 (18)C13—C141.388 (2)
O2—C41.4121 (17)C13—H130.9500
O2—B11.4490 (19)C14—C151.381 (2)
N1—C21.4906 (17)C14—H140.9500
N1—C31.4928 (18)C15—C161.391 (2)
N1—C111.5034 (18)C15—H150.9500
N1—B11.7836 (19)C16—C171.391 (2)
C1—C51.512 (2)C16—H160.9500
C1—C21.5346 (19)C17—H170.9500
C1—H11.0000C18—C231.390 (2)
C2—H2A0.9900C18—C191.392 (2)
C2—H2B0.9900C19—C201.392 (2)
C3—C41.5292 (19)C19—H190.9500
C3—H3A0.9900C20—C211.376 (3)
C3—H3B0.9900C20—H200.9500
C4—C181.503 (2)C21—C221.385 (3)
C4—H41.0000C21—H210.9500
C5—C61.387 (3)C22—C231.391 (2)
C5—C101.396 (2)C22—H220.9500
C6—C71.400 (2)C23—H230.9500
C6—H60.9500C24—C251.339 (2)
C7—C81.378 (3)C24—C271.510 (2)
C7—H70.9500C24—B11.600 (2)
C8—C91.389 (3)C25—C261.507 (2)
C8—H80.9500C25—H250.9500
C9—C101.393 (2)C26—H26A0.9800
C9—H90.9500C26—H26B0.9800
C10—H100.9500C26—H26C0.9800
C11—C121.513 (2)C27—H27A0.9800
C11—H11A0.9900C27—H27B0.9800
C11—H11B0.9900C27—H27C0.9800
C12—C171.393 (2)
C1—O1—B1111.84 (11)C13—C12—C11120.32 (14)
C4—O2—B1111.71 (10)C14—C13—C12120.83 (15)
C2—N1—C3112.32 (11)C14—C13—H13119.6
C2—N1—C11111.90 (11)C12—C13—H13119.6
C3—N1—C11111.88 (11)C15—C14—C13120.42 (14)
C2—N1—B1101.57 (10)C15—C14—H14119.8
C3—N1—B1101.77 (10)C13—C14—H14119.8
C11—N1—B1116.69 (10)C14—C15—C16119.47 (15)
O1—C1—C5111.56 (12)C14—C15—H15120.3
O1—C1—C2104.29 (11)C16—C15—H15120.3
C5—C1—C2110.12 (12)C17—C16—C15120.21 (15)
O1—C1—H1110.2C17—C16—H16119.9
C5—C1—H1110.2C15—C16—H16119.9
C2—C1—H1110.2C16—C17—C12120.83 (14)
N1—C2—C1104.85 (11)C16—C17—H17119.6
N1—C2—H2A110.8C12—C17—H17119.6
C1—C2—H2A110.8C23—C18—C19119.44 (14)
N1—C2—H2B110.8C23—C18—C4120.51 (13)
C1—C2—H2B110.8C19—C18—C4120.02 (14)
H2A—C2—H2B108.9C20—C19—C18120.00 (16)
N1—C3—C4104.21 (11)C20—C19—H19120.0
N1—C3—H3A110.9C18—C19—H19120.0
C4—C3—H3A110.9C21—C20—C19120.26 (16)
N1—C3—H3B110.9C21—C20—H20119.9
C4—C3—H3B110.9C19—C20—H20119.9
H3A—C3—H3B108.9C20—C21—C22120.14 (16)
O2—C4—C18111.30 (11)C20—C21—H21119.9
O2—C4—C3103.52 (11)C22—C21—H21119.9
C18—C4—C3112.56 (11)C21—C22—C23120.00 (17)
O2—C4—H4109.8C21—C22—H22120.0
C18—C4—H4109.8C23—C22—H22120.0
C3—C4—H4109.8C22—C23—C18120.13 (15)
C6—C5—C10119.57 (15)C22—C23—H23119.9
C6—C5—C1121.09 (14)C18—C23—H23119.9
C10—C5—C1119.24 (15)C25—C24—C27122.10 (14)
C5—C6—C7119.63 (19)C25—C24—B1120.07 (14)
C5—C6—H6120.2C27—C24—B1117.50 (12)
C7—C6—H6120.2C24—C25—C26127.89 (16)
C8—C7—C6120.7 (2)C24—C25—H25116.1
C8—C7—H7119.6C26—C25—H25116.1
C6—C7—H7119.6C25—C26—H26A109.5
C7—C8—C9119.85 (16)C25—C26—H26B109.5
C7—C8—H8120.1H26A—C26—H26B109.5
C9—C8—H8120.1C25—C26—H26C109.5
C8—C9—C10119.80 (19)H26A—C26—H26C109.5
C8—C9—H9120.1H26B—C26—H26C109.5
C10—C9—H9120.1C24—C27—H27A109.5
C9—C10—C5120.40 (19)C24—C27—H27B109.5
C9—C10—H10119.8H27A—C27—H27B109.5
C5—C10—H10119.8C24—C27—H27C109.5
N1—C11—C12113.93 (11)H27A—C27—H27C109.5
N1—C11—H11A108.8H27B—C27—H27C109.5
C12—C11—H11A108.8O1—B1—O2113.92 (12)
N1—C11—H11B108.8O1—B1—C24111.78 (12)
C12—C11—H11B108.8O2—B1—C24115.69 (12)
H11A—C11—H11B107.7O1—B1—N199.58 (10)
C17—C12—C13118.22 (14)O2—B1—N198.81 (10)
C17—C12—C11121.46 (13)C24—B1—N1115.36 (11)
B1—O1—C1—C5161.21 (12)C13—C12—C17—C160.6 (2)
B1—O1—C1—C242.37 (15)C11—C12—C17—C16179.73 (13)
C3—N1—C2—C182.70 (14)O2—C4—C18—C2334.66 (18)
C11—N1—C2—C1150.49 (12)C3—C4—C18—C2381.04 (16)
B1—N1—C2—C125.30 (13)O2—C4—C18—C19147.15 (13)
O1—C1—C2—N141.83 (14)C3—C4—C18—C1997.15 (16)
C5—C1—C2—N1161.64 (12)C23—C18—C19—C201.4 (2)
C2—N1—C3—C4134.69 (11)C4—C18—C19—C20176.79 (13)
C11—N1—C3—C498.49 (13)C18—C19—C20—C211.4 (2)
B1—N1—C3—C426.82 (12)C19—C20—C21—C220.3 (3)
B1—O2—C4—C18165.89 (12)C20—C21—C22—C230.7 (3)
B1—O2—C4—C344.74 (14)C21—C22—C23—C180.6 (2)
N1—C3—C4—O243.96 (13)C19—C18—C23—C220.4 (2)
N1—C3—C4—C18164.25 (11)C4—C18—C23—C22177.78 (14)
O1—C1—C5—C65.75 (19)C27—C24—C25—C260.9 (3)
C2—C1—C5—C6109.54 (16)B1—C24—C25—C26174.18 (17)
O1—C1—C5—C10177.91 (13)C1—O1—B1—O279.99 (14)
C2—C1—C5—C1066.80 (18)C1—O1—B1—C24146.54 (12)
C10—C5—C6—C71.1 (2)C1—O1—B1—N124.18 (14)
C1—C5—C6—C7177.39 (16)C4—O2—B1—O1130.03 (12)
C5—C6—C7—C80.6 (3)C4—O2—B1—C2498.38 (14)
C6—C7—C8—C90.2 (3)C4—O2—B1—N125.37 (13)
C7—C8—C9—C100.5 (3)C25—C24—B1—O1138.92 (15)
C8—C9—C10—C50.1 (3)C27—C24—B1—O134.66 (18)
C6—C5—C10—C90.7 (3)C25—C24—B1—O26.3 (2)
C1—C5—C10—C9177.11 (16)C27—C24—B1—O2167.24 (13)
C2—N1—C11—C1256.88 (16)C25—C24—B1—N1108.26 (16)
C3—N1—C11—C1270.16 (15)C27—C24—B1—N178.16 (16)
B1—N1—C11—C12173.24 (11)C2—N1—B1—O12.65 (13)
N1—C11—C12—C1793.60 (16)C3—N1—B1—O1113.36 (11)
N1—C11—C12—C1386.79 (17)C11—N1—B1—O1124.59 (12)
C17—C12—C13—C141.7 (2)C2—N1—B1—O2118.90 (11)
C11—C12—C13—C14178.63 (14)C3—N1—B1—O22.89 (12)
C12—C13—C14—C151.5 (2)C11—N1—B1—O2119.16 (12)
C13—C14—C15—C160.1 (2)C2—N1—B1—C24117.11 (13)
C14—C15—C16—C170.9 (2)C3—N1—B1—C24126.87 (12)
C15—C16—C17—C120.7 (2)C11—N1—B1—C244.82 (16)
(III) (2Z)-6-benzyl-2-buten-2-yl-1,3,6,2-dioxazaborocane top
Crystal data top
C24H32BNO2F(000) = 816
Mr = 377.32Dx = 1.173 Mg m3
Orthorhombic, P212121Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2abCell parameters from 988 reflections
a = 10.5916 (14) Åθ = 2.6–32.0°
b = 11.3683 (15) ŵ = 0.07 mm1
c = 17.747 (2) ÅT = 90 K
V = 2136.8 (5) Å3Block, colourless
Z = 40.32 × 0.16 × 0.13 mm
Data collection top
Bruker SMART APEXII
diffractometer
2773 independent reflections
Radiation source: fine-focus sealed tube2576 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.028
Detector resolution: 8.3 pixels mm-1θmax = 27.5°, θmin = 2.1°
ω scansh = 1313
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
k = 1414
Tmin = 0.988, Tmax = 0.993l = 2323
23473 measured reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.030Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.081H-atom parameters constrained
S = 1.13 w = 1/[σ2(Fo2) + (0.0415P)2 + 0.4322P]
where P = (Fo2 + 2Fc2)/3
2773 reflections(Δ/σ)max < 0.001
256 parametersΔρmax = 0.27 e Å3
0 restraintsΔρmin = 0.16 e Å3
Crystal data top
C24H32BNO2V = 2136.8 (5) Å3
Mr = 377.32Z = 4
Orthorhombic, P212121Mo Kα radiation
a = 10.5916 (14) ŵ = 0.07 mm1
b = 11.3683 (15) ÅT = 90 K
c = 17.747 (2) Å0.32 × 0.16 × 0.13 mm
Data collection top
Bruker SMART APEXII
diffractometer
2773 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
2576 reflections with I > 2σ(I)
Tmin = 0.988, Tmax = 0.993Rint = 0.028
23473 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0300 restraints
wR(F2) = 0.081H-atom parameters constrained
S = 1.13Δρmax = 0.27 e Å3
2773 reflectionsΔρmin = 0.16 e Å3
256 parameters
Special details top

Experimental. Compound III: 72% yield. [α]D25 = 22.5° (c= 4.6, CHCl3); 1H NMR (500 MHz, CCDl3): δ 1.79 (d, J = 7 Hz, 3H), 1.89 (s, 3H), 2.68 (apparent t, J = 11.5 Hz, 1H), 3.23 (dd, J = 11.5 Hz, 1H), 4.01 (d, J = 14 Hz, 1H), 4.08 (d, J = 14.5 Hz, 1H), 4.29 (dd, J = 10.5, 7 Hz, 1H), 4.35 (ap t, J = 7 Hz, 1H), 4.56 (dd, J = 10.5, 8 Hz, 1H), 5.23 (dd, J = 11, 4.5 Hz, 1H), 6.35 (m, J = 6.5 Hz, 1H), 7.16–7.40 (m, 15H);13C NMR (125 MHz, CDCl3): δ 14.54, 15.62, 61.40, 64.98, 67.61, 67.68, 76.39, 125.45, 127.58, 128.46,128.50, 128.89, 129.06, 129.22, 130.35, 130.87, 132.33, 133.67, 134.52, 142.14; 11B NMR (80.25 MHz, CDCl3): δ 15.37.

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
xyzUiso*/Ueq
O10.40574 (10)0.58073 (10)0.47798 (6)0.0165 (2)
O20.49577 (10)0.77688 (10)0.47349 (6)0.0169 (2)
N10.62204 (12)0.60979 (12)0.42669 (7)0.0144 (3)
C10.40705 (15)0.55745 (14)0.39932 (8)0.0161 (3)
H10.38550.63050.37070.019*
C20.54477 (14)0.52282 (14)0.38419 (9)0.0161 (3)
H2A0.56170.44200.40230.019*
H2B0.56380.52680.32960.019*
C30.64364 (15)0.72127 (14)0.38358 (9)0.0170 (3)
H3A0.59060.72340.33770.020*
H3B0.73340.72860.36870.020*
C40.60636 (15)0.81979 (13)0.43787 (9)0.0158 (3)
H40.67440.83040.47630.019*
C50.31901 (14)0.45915 (14)0.37709 (9)0.0165 (3)
C60.29435 (15)0.36581 (15)0.42562 (9)0.0185 (3)
H60.32960.36560.47480.022*
C70.21843 (16)0.27298 (15)0.40248 (10)0.0209 (3)
H70.20120.21000.43620.025*
C80.16748 (15)0.27166 (15)0.33027 (10)0.0205 (3)
H80.11540.20820.31460.025*
C90.19321 (15)0.36348 (16)0.28131 (10)0.0212 (3)
H90.15930.36260.23180.025*
C100.26844 (16)0.45683 (15)0.30443 (9)0.0199 (3)
H100.28560.51950.27060.024*
C110.74222 (14)0.55748 (15)0.45645 (8)0.0164 (3)
H11A0.72110.50830.50070.020*
H11B0.79670.62250.47440.020*
C120.81928 (15)0.48222 (15)0.40129 (9)0.0183 (3)
H120.76370.41760.38230.022*
C130.92803 (17)0.42651 (19)0.44524 (10)0.0292 (4)
H13A0.97170.36940.41310.044*
H13B0.89470.38650.48990.044*
H13C0.98750.48790.46080.044*
C140.87123 (16)0.54906 (16)0.33339 (10)0.0229 (4)
H14A0.93290.49980.30700.034*
H14B0.91230.62150.35050.034*
H14C0.80180.56880.29910.034*
C150.58197 (15)0.93533 (14)0.39873 (9)0.0171 (3)
C160.67459 (17)1.02211 (15)0.39844 (9)0.0208 (3)
H160.75411.00720.42120.025*
C170.6512 (2)1.13097 (16)0.36483 (10)0.0270 (4)
H170.71491.18980.36480.032*
C180.5353 (2)1.15341 (15)0.33154 (10)0.0284 (4)
H180.51911.22780.30920.034*
C190.44299 (18)1.06682 (16)0.33100 (10)0.0258 (4)
H190.36381.08180.30780.031*
C200.46591 (16)0.95779 (16)0.36438 (9)0.0216 (3)
H200.40240.89880.36370.026*
C210.56116 (14)0.63548 (14)0.58135 (8)0.0162 (3)
C220.60831 (16)0.72490 (15)0.62136 (9)0.0201 (3)
H220.61280.79890.59670.024*
C230.65519 (18)0.72065 (17)0.70173 (9)0.0256 (4)
H23A0.60810.77710.73220.038*
H23B0.74530.73980.70300.038*
H23C0.64260.64100.72200.038*
C240.55077 (16)0.51355 (15)0.61543 (9)0.0208 (3)
H24A0.63200.49130.63780.031*
H24B0.52820.45690.57600.031*
H24C0.48540.51360.65450.031*
B10.51150 (16)0.65556 (16)0.49695 (10)0.0155 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0135 (5)0.0199 (5)0.0161 (5)0.0006 (5)0.0021 (4)0.0021 (4)
O20.0154 (5)0.0170 (5)0.0183 (5)0.0007 (4)0.0021 (4)0.0007 (4)
N10.0128 (6)0.0155 (6)0.0150 (6)0.0003 (5)0.0010 (5)0.0002 (5)
C10.0156 (7)0.0174 (7)0.0154 (7)0.0002 (6)0.0015 (6)0.0001 (6)
C20.0165 (7)0.0165 (7)0.0154 (7)0.0009 (6)0.0007 (6)0.0025 (6)
C30.0180 (7)0.0159 (7)0.0170 (7)0.0006 (6)0.0023 (6)0.0024 (6)
C40.0155 (7)0.0164 (7)0.0155 (7)0.0009 (6)0.0001 (6)0.0012 (6)
C50.0126 (6)0.0174 (7)0.0195 (7)0.0021 (6)0.0015 (6)0.0019 (6)
C60.0169 (7)0.0208 (8)0.0178 (7)0.0008 (7)0.0001 (6)0.0010 (6)
C70.0203 (7)0.0184 (7)0.0241 (8)0.0002 (7)0.0027 (7)0.0000 (7)
C80.0151 (7)0.0186 (7)0.0278 (8)0.0004 (6)0.0005 (7)0.0067 (7)
C90.0185 (7)0.0251 (8)0.0201 (8)0.0036 (7)0.0032 (6)0.0029 (7)
C100.0198 (7)0.0214 (8)0.0184 (7)0.0007 (7)0.0003 (6)0.0011 (6)
C110.0133 (7)0.0196 (8)0.0163 (7)0.0029 (6)0.0005 (6)0.0008 (6)
C120.0141 (7)0.0217 (8)0.0192 (8)0.0012 (6)0.0009 (6)0.0036 (7)
C130.0236 (8)0.0395 (10)0.0245 (8)0.0153 (8)0.0024 (7)0.0012 (8)
C140.0212 (8)0.0281 (9)0.0195 (7)0.0002 (7)0.0050 (7)0.0038 (7)
C150.0212 (8)0.0157 (7)0.0145 (7)0.0023 (6)0.0005 (6)0.0022 (6)
C160.0246 (8)0.0201 (8)0.0177 (8)0.0007 (7)0.0010 (6)0.0007 (6)
C170.0390 (10)0.0197 (8)0.0222 (8)0.0035 (8)0.0026 (8)0.0017 (7)
C180.0486 (11)0.0177 (8)0.0188 (8)0.0100 (8)0.0031 (8)0.0028 (7)
C190.0307 (9)0.0288 (9)0.0179 (7)0.0124 (8)0.0009 (7)0.0009 (7)
C200.0224 (8)0.0243 (9)0.0180 (7)0.0036 (7)0.0018 (6)0.0006 (7)
C210.0148 (7)0.0183 (7)0.0156 (7)0.0031 (6)0.0032 (6)0.0006 (6)
C220.0220 (7)0.0212 (8)0.0171 (7)0.0003 (7)0.0022 (6)0.0011 (6)
C230.0280 (9)0.0290 (9)0.0198 (8)0.0051 (8)0.0004 (7)0.0025 (7)
C240.0237 (8)0.0208 (8)0.0178 (7)0.0012 (7)0.0010 (7)0.0012 (6)
B10.0131 (7)0.0174 (8)0.0159 (8)0.0023 (7)0.0027 (6)0.0020 (6)
Geometric parameters (Å, º) top
O1—C11.4208 (18)C12—C131.528 (2)
O1—B11.446 (2)C12—C141.527 (2)
O2—C41.4176 (19)C12—H121.0000
O2—B11.450 (2)C13—H13A0.9800
N1—C21.4885 (19)C13—H13B0.9800
N1—C31.498 (2)C13—H13C0.9800
N1—C111.5010 (19)C14—H14A0.9800
N1—B11.788 (2)C14—H14B0.9800
C1—C51.508 (2)C14—H14C0.9800
C1—C21.535 (2)C15—C161.391 (2)
C1—H11.0000C15—C201.396 (2)
C2—H2A0.9900C16—C171.396 (2)
C2—H2B0.9900C16—H160.9500
C3—C41.529 (2)C17—C181.386 (3)
C3—H3A0.9900C17—H170.9500
C3—H3B0.9900C18—C191.387 (3)
C4—C151.508 (2)C18—H180.9500
C4—H41.0000C19—C201.395 (2)
C5—C61.391 (2)C19—H190.9500
C5—C101.397 (2)C20—H200.9500
C6—C71.389 (2)C21—C221.337 (2)
C6—H60.9500C21—C241.516 (2)
C7—C81.391 (2)C21—B11.604 (2)
C7—H70.9500C22—C231.511 (2)
C8—C91.385 (2)C22—H220.9500
C8—H80.9500C23—H23A0.9765
C9—C101.389 (2)C23—H23B0.9793
C9—H90.9500C23—H23C0.9838
C10—H100.9500C24—H24A0.9800
C11—C121.535 (2)C24—H24B0.9800
C11—H11A0.9900C24—H24C0.9800
C11—H11B0.9900
C1—O1—B1109.31 (12)C14—C12—C11114.67 (14)
C4—O2—B1111.13 (12)C13—C12—H12108.1
C2—N1—C3112.78 (12)C14—C12—H12108.1
C2—N1—C11112.42 (12)C11—C12—H12108.1
C3—N1—C11112.67 (12)C12—C13—H13A109.5
C2—N1—B1100.76 (11)C12—C13—H13B109.5
C3—N1—B1102.12 (11)H13A—C13—H13B109.5
C11—N1—B1115.16 (11)C12—C13—H13C109.5
O1—C1—C5112.89 (13)H13A—C13—H13C109.5
O1—C1—C2103.24 (12)H13B—C13—H13C109.5
C5—C1—C2110.61 (13)C12—C14—H14A109.5
O1—C1—H1110.0C12—C14—H14B109.5
C5—C1—H1110.0H14A—C14—H14B109.5
C2—C1—H1110.0C12—C14—H14C109.5
N1—C2—C1105.28 (12)H14A—C14—H14C109.5
N1—C2—H2A110.7H14B—C14—H14C109.5
C1—C2—H2A110.7C16—C15—C20119.31 (15)
N1—C2—H2B110.7C16—C15—C4119.91 (15)
C1—C2—H2B110.7C20—C15—C4120.76 (15)
H2A—C2—H2B108.8C15—C16—C17120.35 (17)
N1—C3—C4104.98 (12)C15—C16—H16119.8
N1—C3—H3A110.8C17—C16—H16119.8
C4—C3—H3A110.8C18—C17—C16120.15 (17)
N1—C3—H3B110.8C18—C17—H17119.9
C4—C3—H3B110.8C16—C17—H17119.9
H3A—C3—H3B108.8C17—C18—C19119.77 (16)
O2—C4—C15111.32 (13)C17—C18—H18120.1
O2—C4—C3104.02 (12)C19—C18—H18120.1
C15—C4—C3113.08 (12)C18—C19—C20120.32 (17)
O2—C4—H4109.4C18—C19—H19119.8
C15—C4—H4109.4C20—C19—H19119.8
C3—C4—H4109.4C19—C20—C15120.09 (17)
C6—C5—C10119.02 (15)C19—C20—H20120.0
C6—C5—C1121.29 (14)C15—C20—H20120.0
C10—C5—C1119.52 (15)C22—C21—C24120.69 (14)
C7—C6—C5120.35 (15)C22—C21—B1120.69 (15)
C7—C6—H6119.8C24—C21—B1118.60 (14)
C5—C6—H6119.8C21—C22—C23126.86 (16)
C6—C7—C8120.35 (16)C21—C22—H22116.6
C6—C7—H7119.8C23—C22—H22116.6
C8—C7—H7119.8C22—C23—H23A109.5
C9—C8—C7119.58 (16)C22—C23—H23B109.5
C9—C8—H8120.2H23A—C23—H23B109.8
C7—C8—H8120.2C22—C23—H23C109.3
C8—C9—C10120.21 (15)H23A—C23—H23C109.4
C8—C9—H9119.9H23B—C23—H23C109.2
C10—C9—H9119.9C21—C24—H24A109.5
C9—C10—C5120.48 (16)C21—C24—H24B109.5
C9—C10—H10119.8H24A—C24—H24B109.5
C5—C10—H10119.8C21—C24—H24C109.5
N1—C11—C12116.57 (12)H24A—C24—H24C109.5
N1—C11—H11A108.1H24B—C24—H24C109.5
C12—C11—H11A108.1O1—B1—O2113.80 (13)
N1—C11—H11B108.1O1—B1—C21112.82 (13)
C12—C11—H11B108.1O2—B1—C21116.18 (13)
H11A—C11—H11B107.3O1—B1—N1100.00 (11)
C13—C12—C14109.71 (14)O2—B1—N198.73 (11)
C13—C12—C11107.83 (13)C21—B1—N1113.28 (12)
B1—O1—C1—C5166.99 (12)O2—C4—C15—C2034.98 (19)
B1—O1—C1—C247.53 (15)C3—C4—C15—C2081.70 (18)
C3—N1—C2—C184.55 (15)C20—C15—C16—C170.7 (2)
C11—N1—C2—C1146.74 (12)C4—C15—C16—C17177.59 (15)
B1—N1—C2—C123.61 (14)C15—C16—C17—C180.1 (3)
O1—C1—C2—N143.92 (15)C16—C17—C18—C190.7 (3)
C5—C1—C2—N1164.94 (12)C17—C18—C19—C200.6 (3)
C2—N1—C3—C4129.25 (13)C18—C19—C20—C150.2 (3)
C11—N1—C3—C4102.16 (14)C16—C15—C20—C190.8 (2)
B1—N1—C3—C421.96 (14)C4—C15—C20—C19177.45 (15)
B1—O2—C4—C15167.73 (12)C24—C21—C22—C230.4 (3)
B1—O2—C4—C345.65 (15)B1—C21—C22—C23178.18 (15)
N1—C3—C4—O240.96 (14)C1—O1—B1—O274.05 (16)
N1—C3—C4—C15161.87 (13)C1—O1—B1—C21150.83 (12)
O1—C1—C5—C631.7 (2)C1—O1—B1—N130.20 (14)
C2—C1—C5—C683.42 (18)C4—O2—B1—O1134.02 (13)
O1—C1—C5—C10153.15 (14)C4—O2—B1—C2192.43 (15)
C2—C1—C5—C1091.74 (17)C4—O2—B1—N128.97 (14)
C10—C5—C6—C71.3 (2)C22—C21—B1—O1146.68 (15)
C1—C5—C6—C7176.47 (14)C24—C21—B1—O131.95 (19)
C5—C6—C7—C80.8 (2)C22—C21—B1—O212.7 (2)
C6—C7—C8—C90.2 (2)C24—C21—B1—O2165.95 (14)
C7—C8—C9—C100.6 (2)C22—C21—B1—N1100.61 (17)
C8—C9—C10—C50.1 (2)C24—C21—B1—N180.76 (17)
C6—C5—C10—C90.9 (2)C2—N1—B1—O12.22 (14)
C1—C5—C10—C9176.14 (15)C3—N1—B1—O1118.58 (12)
C2—N1—C11—C1246.27 (18)C11—N1—B1—O1118.98 (13)
C3—N1—C11—C1282.50 (17)C2—N1—B1—O2113.98 (12)
B1—N1—C11—C12160.91 (13)C3—N1—B1—O22.37 (14)
N1—C11—C12—C13173.45 (14)C11—N1—B1—O2124.81 (13)
N1—C11—C12—C1464.03 (19)C2—N1—B1—C21122.52 (14)
O2—C4—C15—C16143.24 (15)C3—N1—B1—C21121.12 (14)
C3—C4—C15—C16100.08 (17)C11—N1—B1—C211.32 (18)
(IV) (2Z)-2-buten-2-yl-6-isobutyl-1,3,6,2-dioxazaborocane top
Crystal data top
C27H30BNO2F(000) = 880
Mr = 411.33Dx = 1.224 Mg m3
Dm = 0 Mg m3
Dm measured by not measured
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ybCell parameters from 7925 reflections
a = 9.8152 (4) Åθ = 2.2–30.0°
b = 22.6374 (9) ŵ = 0.08 mm1
c = 10.0469 (4) ÅT = 90 K
β = 90.449 (2)°Block, colourless
V = 2232.26 (16) Å30.34 × 0.27 × 0.17 mm
Z = 4
Data collection top
Make? Model? CCD area-detector
diffractometer
6663 independent reflections
Radiation source: fine-focus sealed tube6078 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.029
ϕ and ω scansθmax = 30.0°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
h = 1313
Tmin = 0.982, Tmax = 0.990k = 3131
25742 measured reflectionsl = 1414
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.095All H-atom parameters refined
S = 1.03 w = 1/[σ2(Fo2) + (0.0652P)2 + 0.2168P]
where P = (Fo2 + 2Fc2)/3
6663 reflections(Δ/σ)max = 0.002
799 parametersΔρmax = 0.34 e Å3
1 restraintΔρmin = 0.20 e Å3
Crystal data top
C27H30BNO2V = 2232.26 (16) Å3
Mr = 411.33Z = 4
Monoclinic, P21Mo Kα radiation
a = 9.8152 (4) ŵ = 0.08 mm1
b = 22.6374 (9) ÅT = 90 K
c = 10.0469 (4) Å0.34 × 0.27 × 0.17 mm
β = 90.449 (2)°
Data collection top
Make? Model? CCD area-detector
diffractometer
6663 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)
6078 reflections with I > 2σ(I)
Tmin = 0.982, Tmax = 0.990Rint = 0.029
25742 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0351 restraint
wR(F2) = 0.095All H-atom parameters refined
S = 1.03Δρmax = 0.34 e Å3
6663 reflectionsΔρmin = 0.20 e Å3
799 parameters
Special details top

Experimental. Compound IV: 79% yield. [α]D25 = 67.7° (c = 4.6, CHCl3); 1H NMR (500 MHz, CCDl3): δ 1.98 (ap t, J = 1.5 Hz, 3H), 2.07 (dd, J = 6.5, 1 Hz, 3H), 2.53 (apparent t, J = 11.5 Hz, 1H), 2.75–2.80 (m, 1H), 2.92 (dd, J = 10.5, 3.5 Hz, 1H), 3.65 (dd, J = 12.5, 4.5 Hz, 1H), 4.01 (d, J = 2 Hz, 2H), 5.19 (dd, J = 10.5, 4.5 Hz, 1H), 5.28 (dd, J = 10.5, 3 Hz, 1H), 6.14 (q, J = 7, Hz, 1H), 7.26–7.41 (m, 15H), 7.51 (dd, J = 13.5, 7.5 Hz, 2H; 13C NMR (125 MHz, δ CDCl3): 17.24, 25.77, 59.60, 60.73, 66.46, 72.52, 73.86, 125.75, 126.03, 127.62, 127.72, 127.82, 128.52, 128.61, 129.14, 129.22, 130.99, 133.23, 134.55, 140.68; 11B NMR (80.25 MHz, CDCl3): δ 14.29.

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
xyzUiso*/Ueq
B10.84702 (18)0.84654 (8)0.91169 (17)0.0152 (3)
C10.91701 (16)0.85668 (7)1.13465 (15)0.0157 (3)
H10.910 (3)0.8133 (11)1.162 (2)0.024 (6)*
N11.02736 (13)0.84304 (6)0.92400 (13)0.0152 (2)
O10.81385 (11)0.87044 (5)1.04033 (11)0.0170 (2)
C21.05124 (16)0.86684 (7)1.06084 (16)0.0160 (3)
H2A1.127 (2)0.8489 (10)1.102 (2)0.015 (5)*
H2B1.066 (2)0.9099 (11)1.056 (2)0.018 (5)*
O20.81905 (12)0.78340 (5)0.89948 (12)0.0180 (2)
C31.05352 (17)0.77796 (7)0.91582 (17)0.0170 (3)
H3A1.142 (2)0.7690 (10)0.878 (2)0.016 (5)*
H3B1.056 (2)0.7600 (10)1.004 (2)0.018 (5)*
C40.93052 (16)0.75459 (7)0.83803 (16)0.0166 (3)
H40.936 (2)0.7668 (11)0.739 (2)0.020 (5)*
C50.90884 (17)0.89632 (7)1.25559 (16)0.0176 (3)
C60.79965 (18)0.93485 (8)1.27311 (17)0.0212 (3)
H60.728 (3)0.9364 (12)1.211 (3)0.028 (6)*
C70.7978 (2)0.97343 (9)1.38152 (19)0.0266 (4)
H70.715 (3)1.0000 (13)1.384 (3)0.036 (7)*
C80.9058 (2)0.97442 (9)1.47134 (18)0.0273 (4)
H80.910 (3)1.0018 (14)1.548 (3)0.036 (7)*
C91.0141 (2)0.93558 (9)1.45604 (18)0.0256 (4)
H91.086 (3)0.9359 (13)1.517 (3)0.036 (7)*
C101.01591 (18)0.89623 (8)1.34859 (17)0.0210 (3)
H101.092 (3)0.8688 (12)1.340 (3)0.027 (6)*
C111.10364 (16)0.87672 (7)0.81873 (16)0.0170 (3)
H11A1.107 (2)0.8503 (11)0.745 (2)0.019 (5)*
H11B1.047 (2)0.9107 (11)0.801 (2)0.020 (5)*
C121.24407 (16)0.89668 (8)0.86214 (16)0.0180 (3)
C131.26605 (19)0.95672 (8)0.88707 (18)0.0235 (3)
H131.191 (3)0.9838 (12)0.870 (2)0.027 (6)*
C141.3920 (2)0.97685 (10)0.9331 (2)0.0293 (4)
H141.405 (3)1.0178 (13)0.954 (3)0.034 (7)*
C151.4974 (2)0.93710 (11)0.95455 (19)0.0316 (4)
H151.583 (3)0.9536 (14)0.987 (3)0.041 (7)*
C161.47766 (18)0.87751 (10)0.92829 (19)0.0270 (4)
H161.552 (3)0.8490 (14)0.941 (3)0.040 (7)*
C171.35201 (17)0.85733 (8)0.88164 (17)0.0213 (3)
H171.338 (2)0.8167 (11)0.861 (2)0.018 (5)*
C180.91950 (17)0.68829 (7)0.84175 (17)0.0183 (3)
C190.94230 (19)0.65537 (8)0.72670 (19)0.0236 (3)
H190.961 (3)0.6763 (12)0.647 (3)0.032 (7)*
C200.9418 (2)0.59371 (8)0.7319 (2)0.0306 (4)
H200.958 (3)0.5701 (13)0.652 (3)0.033 (7)*
C210.9175 (2)0.56509 (9)0.8512 (3)0.0348 (5)
H210.921 (4)0.5212 (17)0.850 (4)0.064 (10)*
C220.8918 (2)0.59782 (9)0.9655 (2)0.0328 (4)
H220.871 (3)0.5799 (14)1.049 (3)0.047 (8)*
C230.8928 (2)0.65925 (8)0.96138 (19)0.0257 (4)
H230.877 (3)0.6835 (12)1.041 (3)0.032 (7)*
C240.79070 (16)0.88559 (7)0.78918 (16)0.0173 (3)
C250.78499 (17)0.94480 (8)0.78419 (17)0.0192 (3)
H250.744 (2)0.9632 (10)0.704 (2)0.015 (5)*
C260.84002 (19)0.98873 (8)0.88305 (19)0.0227 (3)
H26A0.879 (3)0.9714 (13)0.963 (3)0.036 (7)*
H26B0.915 (3)1.0120 (15)0.847 (3)0.048 (8)*
H26C0.765 (3)1.0164 (12)0.902 (3)0.031 (7)*
C270.7291 (2)0.85226 (8)0.67250 (18)0.0251 (4)
H27A0.689 (3)0.8786 (12)0.602 (3)0.028 (6)*
H27B0.797 (3)0.8295 (13)0.628 (3)0.031 (6)*
H27C0.659 (3)0.8238 (12)0.708 (3)0.032 (7)*
B310.35330 (17)0.74185 (8)0.35139 (18)0.0154 (3)
C310.41925 (16)0.73309 (7)0.12748 (15)0.0157 (3)
H310.410 (2)0.7751 (11)0.099 (2)0.023 (6)*
N310.53157 (13)0.74932 (6)0.33795 (13)0.0148 (2)
O310.31930 (11)0.71749 (5)0.22239 (11)0.0170 (2)
C320.55525 (16)0.72547 (7)0.20195 (15)0.0162 (3)
H32A0.633 (2)0.7435 (10)0.159 (2)0.016 (5)*
H32B0.574 (2)0.6831 (10)0.209 (2)0.016 (5)*
O320.31744 (12)0.80432 (5)0.36315 (12)0.0176 (2)
C330.55105 (16)0.81486 (7)0.34473 (16)0.0164 (3)
H33A0.636 (2)0.8252 (10)0.389 (2)0.018 (5)*
H33B0.548 (2)0.8320 (11)0.254 (2)0.022 (6)*
C340.42733 (16)0.83575 (7)0.42324 (16)0.0161 (3)
H340.441 (2)0.8241 (9)0.516 (2)0.012 (5)*
C350.41414 (17)0.69280 (7)0.00726 (16)0.0179 (3)
C360.30865 (18)0.65227 (8)0.01066 (17)0.0220 (3)
H360.235 (3)0.6523 (12)0.050 (3)0.030 (6)*
C370.3119 (2)0.61239 (9)0.11601 (19)0.0257 (4)
H370.238 (3)0.5846 (11)0.127 (2)0.025 (6)*
C380.4210 (2)0.61215 (9)0.20315 (19)0.0277 (4)
H380.426 (3)0.5852 (11)0.274 (3)0.027 (6)*
C390.52525 (19)0.65323 (10)0.18715 (19)0.0273 (4)
H390.602 (3)0.6521 (12)0.248 (3)0.031 (6)*
C400.52172 (19)0.69395 (9)0.08330 (17)0.0230 (3)
H400.594 (2)0.7209 (11)0.073 (2)0.020 (5)*
C410.61279 (16)0.71731 (7)0.44386 (16)0.0168 (3)
H41A0.565 (2)0.6819 (11)0.466 (2)0.019 (5)*
H41B0.612 (2)0.7431 (11)0.522 (2)0.020 (5)*
C420.75474 (16)0.70077 (7)0.40167 (16)0.0165 (3)
C430.78148 (17)0.64198 (7)0.36862 (17)0.0194 (3)
H430.711 (3)0.6138 (11)0.377 (2)0.024 (6)*
C440.90913 (18)0.62481 (9)0.32343 (19)0.0238 (3)
H440.930 (3)0.5832 (13)0.302 (3)0.033 (7)*
C451.01187 (18)0.66639 (9)0.30942 (18)0.0242 (3)
H451.100 (3)0.6564 (14)0.273 (3)0.041 (7)*
C460.98779 (17)0.72500 (9)0.34468 (18)0.0226 (3)
H461.059 (3)0.7546 (12)0.343 (3)0.030 (6)*
C470.86032 (16)0.74196 (8)0.39141 (17)0.0188 (3)
H470.848 (2)0.7834 (12)0.416 (2)0.021 (5)*
C480.40344 (16)0.90129 (7)0.41945 (16)0.0168 (3)
C490.40198 (17)0.93347 (7)0.53761 (17)0.0191 (3)
H490.422 (2)0.9135 (11)0.624 (2)0.022 (5)*
C500.3770 (2)0.99432 (8)0.53569 (18)0.0223 (3)
H500.378 (2)1.0172 (11)0.619 (2)0.021 (5)*
C510.3546 (2)1.02277 (8)0.41508 (19)0.0239 (3)
H510.332 (3)1.0646 (13)0.414 (3)0.034 (7)*
C520.3573 (2)0.99099 (8)0.29654 (18)0.0237 (3)
H520.336 (2)1.0110 (10)0.213 (2)0.018 (5)*
C530.38071 (18)0.93047 (8)0.29832 (17)0.0205 (3)
H530.381 (3)0.9075 (12)0.218 (3)0.027 (6)*
C540.30553 (16)0.70206 (8)0.47593 (16)0.0178 (3)
C550.29691 (17)0.64300 (8)0.47741 (17)0.0203 (3)
H550.261 (3)0.6223 (12)0.558 (3)0.029 (6)*
C560.3382 (2)0.60003 (8)0.3718 (2)0.0246 (3)
H56A0.383 (3)0.6171 (12)0.303 (3)0.030 (6)*
H56B0.399 (3)0.5684 (13)0.410 (3)0.033 (7)*
H56C0.261 (3)0.5766 (15)0.338 (3)0.051 (9)*
C570.2594 (2)0.73447 (9)0.60012 (19)0.0261 (4)
H57A0.218 (3)0.7096 (14)0.665 (3)0.042 (8)*
H57B0.338 (3)0.7541 (12)0.641 (3)0.035 (7)*
H57C0.201 (3)0.7654 (12)0.576 (3)0.029 (6)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
B10.0132 (7)0.0147 (7)0.0178 (7)0.0006 (6)0.0009 (6)0.0005 (6)
C10.0150 (6)0.0165 (7)0.0157 (6)0.0004 (5)0.0008 (5)0.0015 (5)
N10.0152 (6)0.0142 (6)0.0162 (6)0.0006 (5)0.0017 (5)0.0011 (5)
O10.0145 (5)0.0206 (6)0.0161 (5)0.0011 (4)0.0004 (4)0.0000 (4)
C20.0141 (6)0.0182 (7)0.0157 (6)0.0020 (5)0.0005 (5)0.0007 (5)
O20.0154 (5)0.0153 (5)0.0234 (5)0.0005 (4)0.0015 (4)0.0013 (4)
C30.0173 (7)0.0118 (6)0.0219 (7)0.0007 (5)0.0002 (6)0.0008 (6)
C40.0163 (7)0.0144 (7)0.0192 (7)0.0001 (5)0.0001 (5)0.0013 (5)
C50.0190 (7)0.0184 (7)0.0153 (7)0.0036 (6)0.0025 (5)0.0015 (6)
C60.0222 (8)0.0235 (8)0.0180 (7)0.0014 (6)0.0024 (6)0.0003 (6)
C70.0315 (9)0.0250 (9)0.0234 (8)0.0016 (7)0.0061 (7)0.0030 (7)
C80.0363 (10)0.0263 (9)0.0196 (8)0.0083 (8)0.0062 (7)0.0053 (7)
C90.0284 (8)0.0308 (9)0.0176 (7)0.0088 (7)0.0003 (6)0.0003 (7)
C100.0206 (7)0.0238 (8)0.0186 (7)0.0029 (6)0.0001 (6)0.0010 (6)
C110.0155 (6)0.0179 (7)0.0175 (7)0.0008 (6)0.0012 (5)0.0018 (6)
C120.0161 (7)0.0221 (7)0.0160 (7)0.0022 (6)0.0035 (5)0.0001 (6)
C130.0216 (8)0.0233 (8)0.0257 (8)0.0049 (7)0.0067 (6)0.0029 (7)
C140.0280 (9)0.0330 (10)0.0269 (9)0.0129 (8)0.0073 (7)0.0078 (7)
C150.0208 (8)0.0515 (13)0.0225 (8)0.0132 (8)0.0030 (7)0.0006 (8)
C160.0161 (7)0.0403 (11)0.0246 (8)0.0020 (7)0.0018 (6)0.0071 (8)
C170.0175 (7)0.0256 (8)0.0210 (7)0.0010 (6)0.0040 (6)0.0042 (6)
C180.0180 (7)0.0138 (7)0.0229 (8)0.0011 (5)0.0028 (6)0.0010 (6)
C190.0238 (8)0.0193 (8)0.0278 (9)0.0011 (6)0.0018 (6)0.0046 (7)
C200.0311 (10)0.0181 (8)0.0426 (11)0.0033 (7)0.0066 (8)0.0111 (8)
C210.0376 (11)0.0154 (8)0.0510 (13)0.0004 (7)0.0146 (9)0.0001 (8)
C220.0410 (11)0.0210 (9)0.0361 (10)0.0067 (8)0.0109 (9)0.0077 (8)
C230.0326 (9)0.0183 (8)0.0262 (8)0.0036 (7)0.0042 (7)0.0020 (7)
C240.0161 (6)0.0193 (7)0.0164 (7)0.0010 (6)0.0000 (5)0.0017 (5)
C250.0177 (7)0.0209 (8)0.0189 (7)0.0015 (6)0.0008 (6)0.0011 (6)
C260.0249 (8)0.0165 (7)0.0268 (8)0.0019 (6)0.0003 (7)0.0003 (6)
C270.0315 (9)0.0224 (8)0.0212 (8)0.0041 (7)0.0082 (7)0.0055 (7)
B310.0123 (7)0.0156 (7)0.0182 (7)0.0006 (6)0.0011 (6)0.0000 (6)
C310.0150 (6)0.0164 (7)0.0158 (7)0.0000 (5)0.0002 (5)0.0007 (5)
N310.0145 (6)0.0137 (6)0.0162 (6)0.0001 (5)0.0004 (4)0.0007 (5)
O310.0149 (5)0.0192 (5)0.0170 (5)0.0020 (4)0.0013 (4)0.0021 (4)
C320.0146 (6)0.0186 (7)0.0153 (6)0.0007 (6)0.0004 (5)0.0012 (5)
O320.0140 (5)0.0156 (5)0.0231 (6)0.0002 (4)0.0003 (4)0.0025 (4)
C330.0158 (7)0.0129 (6)0.0205 (7)0.0005 (5)0.0000 (5)0.0000 (5)
C340.0156 (7)0.0135 (7)0.0193 (7)0.0001 (5)0.0004 (5)0.0010 (5)
C350.0191 (7)0.0191 (7)0.0153 (7)0.0020 (6)0.0028 (5)0.0009 (6)
C360.0222 (8)0.0239 (8)0.0198 (7)0.0021 (6)0.0021 (6)0.0007 (6)
C370.0287 (9)0.0251 (9)0.0231 (8)0.0048 (7)0.0059 (7)0.0034 (7)
C380.0312 (9)0.0312 (10)0.0207 (8)0.0044 (8)0.0045 (7)0.0082 (7)
C390.0244 (8)0.0365 (10)0.0210 (8)0.0018 (7)0.0022 (7)0.0057 (7)
C400.0224 (8)0.0270 (8)0.0196 (8)0.0014 (7)0.0007 (6)0.0026 (6)
C410.0148 (6)0.0181 (7)0.0174 (7)0.0003 (6)0.0004 (5)0.0019 (6)
C420.0146 (6)0.0186 (7)0.0163 (7)0.0007 (6)0.0012 (5)0.0020 (5)
C430.0189 (7)0.0162 (7)0.0231 (8)0.0012 (6)0.0010 (6)0.0010 (6)
C440.0219 (8)0.0237 (8)0.0257 (8)0.0069 (7)0.0021 (6)0.0029 (7)
C450.0162 (7)0.0332 (9)0.0232 (8)0.0067 (7)0.0010 (6)0.0008 (7)
C460.0148 (7)0.0284 (9)0.0246 (8)0.0001 (6)0.0008 (6)0.0052 (7)
C470.0146 (7)0.0200 (8)0.0217 (7)0.0000 (6)0.0020 (5)0.0017 (6)
C480.0163 (7)0.0140 (7)0.0202 (7)0.0006 (5)0.0006 (5)0.0005 (5)
C490.0214 (7)0.0160 (7)0.0199 (7)0.0000 (6)0.0015 (6)0.0006 (6)
C500.0300 (9)0.0159 (7)0.0210 (8)0.0002 (6)0.0026 (6)0.0027 (6)
C510.0313 (9)0.0151 (7)0.0254 (8)0.0027 (7)0.0030 (7)0.0004 (6)
C520.0298 (9)0.0200 (8)0.0214 (8)0.0031 (7)0.0004 (6)0.0027 (6)
C530.0236 (8)0.0193 (8)0.0186 (7)0.0017 (6)0.0004 (6)0.0020 (6)
C540.0154 (6)0.0218 (7)0.0163 (7)0.0024 (6)0.0016 (5)0.0017 (6)
C550.0184 (7)0.0219 (8)0.0206 (7)0.0011 (6)0.0008 (6)0.0016 (6)
C560.0277 (9)0.0181 (8)0.0281 (9)0.0017 (7)0.0004 (7)0.0008 (7)
C570.0321 (9)0.0257 (9)0.0207 (8)0.0041 (8)0.0080 (7)0.0035 (7)
Geometric parameters (Å, º) top
B1—O11.441 (2)B31—O311.445 (2)
B1—O21.460 (2)B31—O321.462 (2)
B1—C241.610 (2)B31—C541.614 (2)
B1—N11.775 (2)B31—N311.764 (2)
C1—O11.4161 (19)C31—O311.4181 (19)
C1—C51.513 (2)C31—C351.514 (2)
C1—C21.534 (2)C31—C321.535 (2)
C1—H11.02 (2)C31—H310.99 (3)
N1—C21.493 (2)N31—C321.489 (2)
N1—C31.498 (2)N31—C331.498 (2)
N1—C111.508 (2)N31—C411.510 (2)
C2—H2A0.94 (2)C32—H32A0.97 (2)
C2—H2B0.99 (2)C32—H32B0.98 (2)
O2—C41.4193 (19)O32—C341.4226 (19)
C3—C41.528 (2)C33—C341.528 (2)
C3—H3A0.97 (2)C33—H33A0.97 (2)
C3—H3B0.97 (2)C33—H33B0.99 (2)
C4—C181.505 (2)C34—C481.503 (2)
C4—H41.03 (2)C34—H340.98 (2)
C5—C61.394 (2)C35—C361.394 (2)
C5—C101.401 (2)C35—C401.399 (2)
C6—C71.396 (3)C36—C371.392 (2)
C6—H60.94 (3)C36—H360.95 (3)
C7—C81.387 (3)C37—C381.388 (3)
C7—H71.01 (3)C37—H370.97 (3)
C8—C91.389 (3)C38—C391.391 (3)
C8—H80.99 (3)C38—H380.94 (3)
C9—C101.400 (3)C39—C401.393 (3)
C9—H90.93 (3)C39—H390.97 (3)
C10—H100.97 (3)C40—H400.94 (3)
C11—C121.512 (2)C41—C421.507 (2)
C11—H11A0.95 (2)C41—H41A0.96 (2)
C11—H11B0.96 (2)C41—H41B0.98 (2)
C12—C171.397 (2)C42—C431.397 (2)
C12—C131.399 (2)C42—C471.398 (2)
C13—C141.393 (3)C43—C441.391 (2)
C13—H130.97 (3)C43—H430.94 (3)
C14—C151.387 (3)C44—C451.387 (3)
C14—H140.96 (3)C44—H440.99 (3)
C15—C161.388 (3)C45—C461.394 (3)
C15—H150.97 (3)C45—H450.97 (3)
C16—C171.393 (3)C46—C471.394 (2)
C16—H160.98 (3)C46—H460.97 (3)
C17—H170.95 (2)C47—H470.98 (3)
C18—C191.395 (2)C48—C491.393 (2)
C18—C231.397 (3)C48—C531.401 (2)
C19—C201.397 (3)C49—C501.399 (2)
C19—H190.95 (3)C49—H490.99 (2)
C20—C211.385 (3)C50—C511.388 (3)
C20—H200.98 (3)C50—H500.99 (2)
C21—C221.391 (3)C51—C521.392 (3)
C21—H210.99 (4)C51—H510.97 (3)
C22—C231.391 (3)C52—C531.389 (2)
C22—H220.95 (3)C52—H520.97 (2)
C23—H230.98 (3)C53—H530.96 (3)
C24—C251.343 (2)C54—C551.340 (2)
C24—C271.516 (2)C54—C571.519 (2)
C25—C261.503 (2)C55—C561.498 (3)
C25—H250.99 (2)C55—H551.00 (3)
C26—H26A0.97 (3)C56—H56A0.91 (3)
C26—H26B0.97 (3)C56—H56B1.00 (3)
C26—H26C0.99 (3)C56—H56C0.98 (3)
C27—H27A1.01 (3)C57—H57A0.95 (3)
C27—H27B0.96 (3)C57—H57B0.98 (3)
C27—H27C1.01 (3)C57—H57C0.94 (3)
O1—B1—O2113.52 (13)O31—B31—O32112.79 (14)
O1—B1—C24113.64 (13)O31—B31—C54114.57 (13)
O2—B1—C24114.21 (13)O32—B31—C54113.92 (13)
O1—B1—N1100.74 (11)O31—B31—N31100.96 (11)
O2—B1—N198.56 (11)O32—B31—N3198.80 (11)
C24—B1—N1114.46 (12)C54—B31—N31114.02 (12)
O1—C1—C5111.40 (13)O31—C31—C35111.58 (13)
O1—C1—C2104.82 (12)O31—C31—C32104.35 (12)
C5—C1—C2110.51 (13)C35—C31—C32110.15 (13)
O1—C1—H1109.9 (14)O31—C31—H31111.7 (14)
C5—C1—H1110.7 (14)C35—C31—H31110.3 (14)
C2—C1—H1109.3 (14)C32—C31—H31108.6 (14)
C2—N1—C3112.31 (12)C32—N31—C33112.34 (12)
C2—N1—C11112.84 (12)C32—N31—C41112.79 (12)
C3—N1—C11111.87 (12)C33—N31—C41112.14 (12)
C2—N1—B1101.38 (11)C32—N31—B31101.39 (11)
C3—N1—B1102.20 (11)C33—N31—B31102.58 (11)
C11—N1—B1115.40 (12)C41—N31—B31114.75 (11)
C1—O1—B1110.63 (12)C31—O31—B31110.61 (12)
N1—C2—C1105.17 (12)N31—C32—C31105.37 (12)
N1—C2—H2A111.6 (13)N31—C32—H32A112.5 (13)
C1—C2—H2A113.7 (13)C31—C32—H32A115.0 (13)
N1—C2—H2B109.7 (14)N31—C32—H32B108.8 (13)
C1—C2—H2B107.1 (14)C31—C32—H32B107.9 (13)
H2A—C2—H2B109.5 (19)H32A—C32—H32B107.1 (19)
C4—O2—B1109.95 (12)C34—O32—B31109.62 (12)
N1—C3—C4103.51 (13)N31—C33—C34103.20 (12)
N1—C3—H3A112.4 (14)N31—C33—H33A111.6 (14)
C4—C3—H3A115.7 (13)C34—C33—H33A112.0 (14)
N1—C3—H3B111.4 (14)N31—C33—H33B110.0 (14)
C4—C3—H3B109.7 (13)C34—C33—H33B109.6 (14)
H3A—C3—H3B104.3 (19)H33A—C33—H33B110 (2)
O2—C4—C18113.06 (13)O32—C34—C48111.43 (13)
O2—C4—C3103.13 (13)O32—C34—C33103.24 (12)
C18—C4—C3112.91 (13)C48—C34—C33114.64 (13)
O2—C4—H4109.9 (14)O32—C34—H34111.7 (12)
C18—C4—H4107.1 (14)C48—C34—H34108.1 (12)
C3—C4—H4110.8 (14)C33—C34—H34107.7 (12)
C6—C5—C10119.36 (16)C36—C35—C40119.45 (16)
C6—C5—C1121.20 (15)C36—C35—C31121.29 (15)
C10—C5—C1119.37 (15)C40—C35—C31119.15 (15)
C5—C6—C7120.28 (17)C37—C36—C35120.23 (17)
C5—C6—H6121.1 (16)C37—C36—H36120.7 (16)
C7—C6—H6118.6 (16)C35—C36—H36119.1 (16)
C8—C7—C6120.22 (18)C38—C37—C36120.32 (17)
C8—C7—H7125.6 (17)C38—C37—H37120.5 (15)
C6—C7—H7114.2 (17)C36—C37—H37119.2 (15)
C7—C8—C9119.97 (17)C37—C38—C39119.65 (17)
C7—C8—H8122.8 (17)C37—C38—H38121.6 (16)
C9—C8—H8117.2 (17)C39—C38—H38118.8 (16)
C8—C9—C10120.14 (17)C38—C39—C40120.42 (17)
C8—C9—H9120.1 (18)C38—C39—H39118.8 (16)
C10—C9—H9119.7 (18)C40—C39—H39120.8 (16)
C9—C10—C5119.98 (17)C39—C40—C35119.88 (17)
C9—C10—H10119.3 (16)C39—C40—H40119.2 (14)
C5—C10—H10120.7 (15)C35—C40—H40120.8 (14)
N1—C11—C12113.92 (13)C42—C41—N31113.91 (13)
N1—C11—H11A104.6 (14)C42—C41—H41A108.4 (14)
C12—C11—H11A111.9 (14)N31—C41—H41A107.9 (14)
N1—C11—H11B104.2 (14)C42—C41—H41B112.9 (14)
C12—C11—H11B109.5 (14)N31—C41—H41B105.8 (14)
H11A—C11—H11B112 (2)H41A—C41—H41B107.6 (19)
C17—C12—C13118.62 (16)C43—C42—C47118.49 (15)
C17—C12—C11122.59 (16)C43—C42—C41118.65 (14)
C13—C12—C11118.77 (15)C47—C42—C41122.85 (15)
C14—C13—C12120.84 (18)C44—C43—C42121.00 (16)
C14—C13—H13121.4 (15)C44—C43—H43120.2 (15)
C12—C13—H13117.8 (16)C42—C43—H43118.8 (15)
C15—C14—C13119.87 (19)C45—C44—C43120.05 (17)
C15—C14—H14119.8 (17)C45—C44—H44118.4 (16)
C13—C14—H14120.3 (17)C43—C44—H44121.6 (16)
C14—C15—C16119.92 (18)C44—C45—C46119.68 (16)
C14—C15—H15116.3 (18)C44—C45—H45122.1 (18)
C16—C15—H15123.8 (18)C46—C45—H45118.2 (18)
C15—C16—C17120.30 (19)C47—C46—C45120.16 (16)
C15—C16—H16120.8 (18)C47—C46—H46117.7 (16)
C17—C16—H16118.9 (18)C45—C46—H46122.0 (16)
C16—C17—C12120.43 (18)C46—C47—C42120.58 (16)
C16—C17—H17120.9 (14)C46—C47—H47117.8 (14)
C12—C17—H17118.7 (14)C42—C47—H47121.6 (14)
C19—C18—C23119.60 (16)C49—C48—C53119.42 (15)
C19—C18—C4120.01 (16)C49—C48—C34119.82 (15)
C23—C18—C4120.32 (15)C53—C48—C34120.75 (14)
C18—C19—C20120.15 (19)C48—C49—C50120.39 (16)
C18—C19—H19117.8 (16)C48—C49—H49120.0 (14)
C20—C19—H19122.0 (16)C50—C49—H49119.6 (14)
C21—C20—C19120.03 (19)C51—C50—C49119.70 (16)
C21—C20—H20119.1 (17)C51—C50—H50120.0 (14)
C19—C20—H20120.9 (17)C49—C50—H50120.3 (14)
C20—C21—C22119.92 (18)C50—C51—C52120.20 (16)
C20—C21—H21117 (2)C50—C51—H51120.0 (16)
C22—C21—H21123 (2)C52—C51—H51119.7 (16)
C23—C22—C21120.4 (2)C53—C52—C51120.20 (17)
C23—C22—H22117 (2)C53—C52—H52120.3 (14)
C21—C22—H22123 (2)C51—C52—H52119.4 (14)
C22—C23—C18119.85 (19)C52—C53—C48120.09 (16)
C22—C23—H23122.4 (16)C52—C53—H53121.6 (15)
C18—C23—H23117.8 (16)C48—C53—H53118.3 (15)
C25—C24—C27116.86 (15)C55—C54—C57116.97 (15)
C25—C24—B1126.22 (15)C55—C54—B31125.74 (15)
C27—C24—B1116.77 (14)C57—C54—B31117.21 (15)
C24—C25—C26128.40 (16)C54—C55—C56128.53 (16)
C24—C25—H25117.9 (13)C54—C55—H55119.9 (15)
C26—C25—H25113.7 (13)C56—C55—H55111.6 (15)
C25—C26—H26A114.8 (17)C55—C56—H56A113.3 (17)
C25—C26—H26B112.4 (19)C55—C56—H56B110.9 (16)
H26A—C26—H26B103 (3)H56A—C56—H56B108 (2)
C25—C26—H26C106.5 (16)C55—C56—H56C112 (2)
H26A—C26—H26C112 (2)H56A—C56—H56C110 (3)
H26B—C26—H26C107 (3)H56B—C56—H56C102 (3)
C24—C27—H27A113.8 (15)C54—C57—H57A113.9 (19)
C24—C27—H27B110.8 (16)C54—C57—H57B109.2 (17)
H27A—C27—H27B105 (2)H57A—C57—H57B108 (3)
C24—C27—H27C108.3 (16)C54—C57—H57C109.3 (16)
H27A—C27—H27C111 (2)H57A—C57—H57C111 (3)
H27B—C27—H27C107 (2)H57B—C57—H57C104 (2)
O1—B1—N1—C20.20 (14)O31—B31—N31—C321.19 (14)
O2—B1—N1—C2116.27 (12)O32—B31—N31—C32116.61 (13)
C24—B1—N1—C2122.13 (14)C54—B31—N31—C32122.19 (14)
O1—B1—N1—C3115.88 (13)O31—B31—N31—C33115.06 (13)
O2—B1—N1—C30.18 (14)O32—B31—N31—C330.36 (14)
C24—B1—N1—C3121.79 (14)C54—B31—N31—C33121.56 (14)
O1—B1—N1—C11122.47 (13)O31—B31—N31—C41123.06 (13)
O2—B1—N1—C11121.46 (13)O32—B31—N31—C41121.52 (13)
C24—B1—N1—C110.15 (18)C54—B31—N31—C410.31 (18)
C5—C1—O1—B1161.91 (13)C35—C31—O31—B31160.77 (13)
C2—C1—O1—B142.37 (16)C32—C31—O31—B3141.86 (16)
O2—B1—O1—C178.80 (16)O32—B31—O31—C3179.68 (16)
C24—B1—O1—C1148.45 (13)C54—B31—O31—C31147.81 (13)
N1—B1—O1—C125.55 (15)N31—B31—O31—C3124.82 (15)
C3—N1—C2—C185.37 (15)C33—N31—C32—C3184.88 (15)
C11—N1—C2—C1147.05 (13)C41—N31—C32—C31147.20 (13)
B1—N1—C2—C123.03 (14)B31—N31—C32—C3123.98 (14)
O1—C1—C2—N140.46 (15)O31—C31—C32—N3140.88 (15)
C5—C1—C2—N1160.59 (13)C35—C31—C32—N31160.76 (13)
O1—B1—O2—C4134.78 (14)O31—B31—O32—C34134.66 (13)
C24—B1—O2—C492.75 (15)C54—B31—O32—C3492.51 (15)
N1—B1—O2—C429.04 (14)N31—B31—O32—C3428.77 (14)
C2—N1—C3—C4134.01 (13)C32—N31—C33—C34134.35 (13)
C11—N1—C3—C497.90 (14)C41—N31—C33—C3497.39 (14)
B1—N1—C3—C426.14 (14)B31—N31—C33—C3426.25 (14)
B1—O2—C4—C18170.74 (13)B31—O32—C34—C48171.79 (13)
B1—O2—C4—C348.49 (16)B31—O32—C34—C3348.25 (15)
N1—C3—C4—O245.64 (15)N31—C33—C34—O3245.59 (15)
N1—C3—C4—C18168.00 (13)N31—C33—C34—C48166.98 (13)
O1—C1—C5—C68.0 (2)O31—C31—C35—C368.9 (2)
C2—C1—C5—C6124.15 (16)C32—C31—C35—C36124.33 (17)
O1—C1—C5—C10169.05 (14)O31—C31—C35—C40167.25 (15)
C2—C1—C5—C1052.95 (19)C32—C31—C35—C4051.8 (2)
C10—C5—C6—C70.7 (3)C40—C35—C36—C371.5 (3)
C1—C5—C6—C7176.36 (16)C31—C35—C36—C37174.69 (16)
C5—C6—C7—C81.1 (3)C35—C36—C37—C380.8 (3)
C6—C7—C8—C92.1 (3)C36—C37—C38—C392.0 (3)
C7—C8—C9—C101.3 (3)C37—C38—C39—C400.9 (3)
C8—C9—C10—C50.5 (3)C38—C39—C40—C351.3 (3)
C6—C5—C10—C91.6 (2)C36—C35—C40—C392.5 (3)
C1—C5—C10—C9175.60 (15)C31—C35—C40—C39173.73 (17)
C2—N1—C11—C1237.64 (18)C32—N31—C41—C4238.83 (18)
C3—N1—C11—C1290.17 (16)C33—N31—C41—C4289.20 (16)
B1—N1—C11—C12153.55 (13)B31—N31—C41—C42154.27 (13)
N1—C11—C12—C1770.3 (2)N31—C41—C42—C43104.02 (17)
N1—C11—C12—C13107.99 (17)N31—C41—C42—C4774.6 (2)
C17—C12—C13—C141.4 (3)C47—C42—C43—C441.5 (2)
C11—C12—C13—C14177.05 (16)C41—C42—C43—C44177.14 (16)
C12—C13—C14—C150.1 (3)C42—C43—C44—C450.6 (3)
C13—C14—C15—C160.9 (3)C43—C44—C45—C462.0 (3)
C14—C15—C16—C170.6 (3)C44—C45—C46—C471.2 (3)
C15—C16—C17—C120.7 (3)C45—C46—C47—C420.9 (3)
C13—C12—C17—C161.7 (2)C43—C42—C47—C462.3 (2)
C11—C12—C17—C16176.68 (15)C41—C42—C47—C46176.33 (15)
O2—C4—C18—C19132.61 (16)O32—C34—C48—C49122.06 (16)
C3—C4—C18—C19110.79 (18)C33—C34—C48—C49121.15 (17)
O2—C4—C18—C2350.4 (2)O32—C34—C48—C5357.1 (2)
C3—C4—C18—C2366.2 (2)C33—C34—C48—C5359.7 (2)
C23—C18—C19—C201.6 (3)C53—C48—C49—C500.5 (2)
C4—C18—C19—C20175.39 (17)C34—C48—C49—C50178.64 (16)
C18—C19—C20—C210.6 (3)C48—C49—C50—C510.5 (3)
C19—C20—C21—C220.8 (3)C49—C50—C51—C520.2 (3)
C20—C21—C22—C231.2 (3)C50—C51—C52—C530.8 (3)
C21—C22—C23—C180.2 (3)C51—C52—C53—C480.8 (3)
C19—C18—C23—C221.2 (3)C49—C48—C53—C520.2 (3)
C4—C18—C23—C22175.77 (18)C34—C48—C53—C52179.31 (16)
O1—B1—C24—C2537.3 (2)O31—B31—C54—C5531.7 (2)
O2—B1—C24—C25169.71 (16)O32—B31—C54—C55163.70 (16)
N1—B1—C24—C2577.7 (2)N31—B31—C54—C5583.9 (2)
O1—B1—C24—C27138.07 (16)O31—B31—C54—C57144.98 (15)
O2—B1—C24—C275.7 (2)O32—B31—C54—C5713.0 (2)
N1—B1—C24—C27106.92 (16)N31—B31—C54—C5799.38 (17)
C27—C24—C25—C26178.45 (17)C57—C54—C55—C56178.15 (17)
B1—C24—C25—C266.2 (3)B31—C54—C55—C565.1 (3)

Experimental details

(II)(III)(IV)
Crystal data
Chemical formulaC27H30BNO2C24H32BNO2C27H30BNO2
Mr411.33377.32411.33
Crystal system, space groupOrthorhombic, P212121Orthorhombic, P212121Monoclinic, P21
Temperature (K)909090
a, b, c (Å)12.0141 (4), 12.3388 (5), 15.6913 (6)10.5916 (14), 11.3683 (15), 17.747 (2)9.8152 (4), 22.6374 (9), 10.0469 (4)
α, β, γ (°)90, 90, 9090, 90, 9090, 90.449 (2), 90
V3)2326.07 (15)2136.8 (5)2232.26 (16)
Z444
Radiation typeMo KαMo KαMo Kα
µ (mm1)0.070.070.08
Crystal size (mm)0.40 × 0.04 × 0.030.32 × 0.16 × 0.130.34 × 0.27 × 0.17
Data collection
DiffractometerBruker SMART APEXII
diffractometer
Bruker SMART APEXII
diffractometer
Make? Model? CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2004)
Multi-scan
(SADABS; Sheldrick, 2004)
Multi-scan
(SADABS; Sheldrick, 2004)
Tmin, Tmax0.990, 0.9980.988, 0.9930.982, 0.990
No. of measured, independent and
observed [I > 2σ(I)] reflections
32109, 3885, 3493 23473, 2773, 2576 25742, 6663, 6078
Rint0.0300.0280.029
(sin θ/λ)max1)0.7100.6490.703
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.037, 0.099, 1.03 0.030, 0.081, 1.13 0.035, 0.095, 1.03
No. of reflections388527736663
No. of parameters282256799
No. of restraints001
H-atom treatmentH-atom parameters constrainedH-atom parameters constrainedAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.26, 0.160.27, 0.160.34, 0.20

Computer programs: APEX2 (Bruker, 2004), SMART (Bruker, 2003), SAINT (Bruker, 2004), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), XP in SHELXTL (Sheldrick, 1994), SHELXL97.

Selected bond lengths (Å) for (II) top
O1—B11.4469 (18)N1—C111.5034 (18)
O2—B11.4490 (19)N1—B11.7836 (19)
N1—C21.4906 (17)C24—B11.600 (2)
N1—C31.4928 (18)
Selected bond lengths (Å) for (III) top
O1—B11.446 (2)N1—C111.5010 (19)
O2—B11.450 (2)N1—B11.788 (2)
N1—C21.4885 (19)C21—B11.604 (2)
N1—C31.498 (2)
Selected bond lengths (Å) for (IV) top
B1—O11.441 (2)B31—O311.445 (2)
B1—O21.460 (2)B31—O321.462 (2)
B1—C241.610 (2)B31—C541.614 (2)
B1—N11.775 (2)B31—N311.764 (2)
N1—C21.493 (2)N31—C321.489 (2)
N1—C31.498 (2)N31—C331.498 (2)
N1—C111.508 (2)N31—C411.510 (2)
 

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