Allyl 3,4,6-tri-O-acetyl-2-de­oxy-2-phthalimido-β-d-gluco­pyran­oside

Curran, H.; Zhang, C.; Piro, N.A.; Kassel, W.S.; Giuliano, R.M.

doi:10.1107/S2414314616013638

organic compounds

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ISSN: 2414-3146

Volume 1| Part 8| August 2016| x161363

doi:10.1107/S2414314616013638

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Allyl 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-β-D-glucopyranoside

Hannah Curran,^a Chenyao Zhang,^a Nicholas A. Piro,^a W. Scott Kassel ^a and Robert M. Giuliano ^a ^*

^aDepartment of Chemistry, Villanova University, 800 E Lancaster Avenue, Villanova, PA, USA
^*Correspondence e-mail: robert.giuliano@villanova.edu

Edited by A. J. Lough, University of Toronto, Canada (Received 13 August 2016; accepted 24 August 2016; online 31 August 2016)

The protected glycoside of 2-amino-2-deoxyglucose (glucosamine), namely allyl 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-β-D-glucopyranoside, C₂₃H₂₅NO₁₀, was synthesized from the glycosyl bromide. Crystallographic analysis confirmed the β-anomeric configuration and showed an approximately orthogonal orientation of the phthalimido group with respect to the pyranose ring. The absolute configuration of the molecule was known from the synthetic route and assigned accordingly.

Keywords: crystal structure; carbohydrate; allyl glycoside; N-acetylglucosamine; GlcNAc.

CCDC reference: 1500891

Structure description

Aside from its presence in chitin, the second most abundant biopolymer in nature, N-acetylglucosamine (GlcNAc) occurs widely in glycans and bioconjugates in both α- and β-linked glycosides as well as in other biologically important substances such as heparins and tunicamycins (Stick & Williams, 2009 ; Kerns & Wei, 2012 ; Lindhorst, 2003 ). Owing to the role of GlcNAc-containing glycosides in biologically active materials and cell surface glycans, there has been much interest in their chemical synthesis (Ibid.). The title allyl glycoside (1) has been used previously as an intermediate in the synthesis of oligosaccharide haptens of Streptococci Group A cell-wall polysaccharides (Pinto et al., 1991 ) and its analogous tert-butyl glycoside was used in a synthetic program aimed at gangliotriosylceramide, a tumor-specific cell-surface marker (Wessel et al., 1984 ). Our interest in the synthesis of the lipid A disaccharide (Johnson et al., 1999 ), which is comprised of two β-(1→6) linked GlcNAc units, required the preparation of allyl glycoside 1 for use as an intermediate. The synthesis of 1 was reported using a ferric chloride-catalyzed glycosidation of allyl alcohol with 1,3,4,6-tetra-O-acetyl-2-deoxy-2-phthalimido-β-D-glucopyranoside (Kiso & Anderson, 1985 ). Other syntheses have been reported (Miquel et al., 2004 ). Our route was based on a modification in which the glycosidation of allyl alcohol with 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl bromide occurred in the presence of silver trifluoromethanesulfonate and tetramethylurea (Hanessian & Banoub, 1977a ,b ) in high yield and stereoselectivity. Chromatographic purification of 1 gave product suitable for crystallographic analysis.

The pyranose ring of 1 adopts a chair conformation with little evidence of distortion or puckering (Fig. 1). The N1—C2—C1—O2 and N1—C2—C3—O3 torsion angles are −65.2 (2) and 66.4 (2)°, respectively, corresponding to gauche relationships between the C1 allyloxy group and the C2 phthalimido group and between the C2 phthalimido group and the C3 acetoxy group. The phthalimido group is approximately orthogonal to a plane that bisects the pyranose ring at C2 and C5. The stereoselectivity for the formation of the 1,2-trans product in glycosidations of sugars that have a phthalimido group at C2 is ascribed to the steric hindrance that this relatively large group provides on the α-face of the pyranose ring (Stick & Williams, 2009) or through neighboring group participation involving a phthalimide carbonyl group (Lindhorst, 2003).

Figure 1
Two views of the molecular structure of allyl 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-β-D-glucopyranoside with displacement ellipsoids at the 40% probability level.

Synthesis and crystallization

Allyl 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-β-D-glucopyranoside 1.

To a stirring solution of 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-β-D-glucopyranosyl bromide (0.704 g, 1.41 mmol) (Lemieux et al., 1977 ) in anhydrous dichloromethane (10 ml) was added allyl alcohol (0.812 g, 0.953 ml, 14 mmol), tetramethylurea (0.205 g, 0.211 ml, 1.77 mmol), and silver trifluoromethanesulfonate (0.398 mg, 1.55 mmol, dried by evaporation from benzene and high vacuum). The flask was wrapped with aluminium foil and the reaction stirred at room temperature. Progress of the reaction was monitored by thin-layer chromatography on aluminium-backed silica gel plates visualized with Hanessian stain. After 3 h dichloromethane (25 ml) was added and solids were removed by filtration through a pad of Celite. The filtrate was transferred to a separatory funnel and washed with saturated aqueous NaHCO₃ solution, saturated aqueous NaCl solution, dried (Na₂SO₄), and concentrated under reduced pressure to give crude product that was purified by flash chromatography (Still et al., 1978 ) with 40% ethyl acetate/hexane to give crystalline allyl glycoside; yield, 0.46 g (69%): R_f 0.26 (40% ethyl acetate-hexanes), m.p. 379–381 K, lit. m.p. 382–383 K (Kiso & Anderson, 1985), [α]_D +39.7 (c, 1.0, chloroform, lit^. [α]_D +37 (Ibid.). The ¹H NMR data for 1 matched that reported (Ibid.)

Refinement

The absolute configuration of the molecule was known from the synthetic route and set consistent with this information. Upon initial refinement, poorly shaped displacement ellipsoids suggested a possible positional disorder of the allyl group. Attempts to refine this disorder were unsuccessful, and so the displacement parameters of allyl group atoms (C7, C8, C9) were refined with the aid of rigid bond restraints and similarity restraints on the anisotropic displacement parameters of nearby atoms, as well as a weak restraint to encourage approximately isotropic behavior. Additional crystal data, data collection and structure refinement details are summarized in Table 1.

Table 1
Experimental details

Crystal data
Chemical formula	C₂₃H₂₅NO₁₀
M_r	475.44
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	100
a, b, c (Å)	5.6873 (1), 13.8090 (3), 29.7776 (6)
V (Å³)	2338.61 (8)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.11
Crystal size (mm)	0.15 × 0.15 × 0.10

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2014 )
T_min, T_max	0.691, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	46038, 5380, 4500
R_int	0.062
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.077, 1.03
No. of reflections	5380
No. of parameters	310
No. of restraints	41
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.18
Absolute structure	Flack x determined using 1685 quotients [(I⁺)−(I⁻)]/[(I⁺)+(I⁻)] (Parsons et al., 2013 )
Absolute structure parameter	−0.6 (4)
Computer programs: APEX2 and SAINT (Bruker, 2013 ), SHELXT (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ) and OLEX2 (Dolomanov et al., 2009 ).

Structural data

CCDC reference: 1500891

Crystal structure: contains datablock I. DOI: 10.1107/S2414314616013638/lh4012sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S2414314616013638/lh4012Isup2.hkl

Supporting information file. DOI: 10.1107/S2414314616013638/lh4012Isup3.cdx

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); program(s) used to solve structure: SHELXT (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Allyl 3,4,6-tri-O-acetyl-2-deoxy-2-phthalimido-β-D-glucopyranoside top

Crystal data top

C₂₃H₂₅NO₁₀	D_x = 1.350 Mg m⁻³
M_r = 475.44	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 7270 reflections
a = 5.6873 (1) Å	θ = 2.5–23.4°
b = 13.8090 (3) Å	µ = 0.11 mm⁻¹
c = 29.7776 (6) Å	T = 100 K
V = 2338.61 (8) Å³	Block, colourless
Z = 4	0.15 × 0.15 × 0.10 mm
F(000) = 1000

Data collection top

Bruker APEXII CCD diffractometer	5380 independent reflections
Radiation source: sealed tube	4500 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.062
Detector resolution: 8 pixels mm^-1	θ_max = 27.5°, θ_min = 1.6°
ω and φ scans	h = −7→7
Absorption correction: multi-scan (SADABS; Bruker, 2014)	k = −17→17
T_min = 0.691, T_max = 0.746	l = −38→38
46038 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.036	w = 1/[σ²(F_o²) + (0.0288P)² + 0.5249P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.077	(Δ/σ)_max = 0.001
S = 1.03	Δρ_max = 0.20 e Å⁻³
5380 reflections	Δρ_min = −0.18 e Å⁻³
310 parameters	Absolute structure: Flack x determined using 1685 quotients [(I⁺)-(I^-)]/[(I⁺)+(I^-)] (Parsons et al., 2013)
41 restraints	Absolute structure parameter: −0.6 (4)
Primary atom site location: structure-invariant direct methods

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
O3	0.2553 (3)	0.46285 (10)	0.67489 (5)	0.0204 (3)
O5	0.5381 (3)	0.12299 (11)	0.65519 (5)	0.0242 (4)
O4	0.5249 (3)	0.31082 (11)	0.71755 (5)	0.0222 (3)
O1	0.6786 (3)	0.28757 (10)	0.59977 (5)	0.0231 (4)
O10	0.8145 (3)	0.59507 (11)	0.62906 (5)	0.0257 (4)
O9	0.1351 (3)	0.53828 (12)	0.55059 (5)	0.0266 (4)
O2	0.6391 (3)	0.38688 (11)	0.53945 (5)	0.0277 (4)
O6	0.7384 (3)	−0.01621 (11)	0.66104 (6)	0.0316 (4)
O8	0.4357 (3)	0.54328 (14)	0.73116 (6)	0.0336 (4)
O7	0.1550 (3)	0.25372 (14)	0.72336 (6)	0.0379 (5)
N1	0.4727 (3)	0.54214 (13)	0.59438 (6)	0.0193 (4)
C19	0.6429 (4)	0.61102 (16)	0.60621 (7)	0.0211 (5)
C16	0.2979 (4)	0.58224 (16)	0.56677 (7)	0.0206 (5)
C2	0.4748 (4)	0.44030 (15)	0.60714 (7)	0.0201 (5)
H2	0.3260	0.4107	0.5956	0.024*
C10	0.2579 (4)	0.51553 (16)	0.71358 (7)	0.0225 (5)
C1	0.6795 (4)	0.38592 (16)	0.58531 (7)	0.0226 (5)
H1	0.8328	0.4177	0.5926	0.027*
C14	0.5528 (4)	0.02604 (16)	0.65995 (8)	0.0229 (5)
C3	0.4764 (4)	0.42761 (15)	0.65811 (7)	0.0193 (4)
H3	0.6093	0.4650	0.6717	0.023*
C4	0.4985 (4)	0.32114 (15)	0.66975 (7)	0.0196 (5)
H4	0.3549	0.2856	0.6595	0.023*
C17	0.3591 (4)	0.68644 (16)	0.56204 (7)	0.0215 (5)
C18	0.5673 (4)	0.70329 (16)	0.58524 (7)	0.0211 (5)
C23	0.6683 (4)	0.79430 (16)	0.58652 (8)	0.0255 (5)
H23	0.8093	0.8060	0.6027	0.031*
C5	0.7146 (4)	0.27908 (16)	0.64710 (7)	0.0219 (5)
H5	0.8556	0.3181	0.6558	0.026*
C12	0.3393 (5)	0.27364 (16)	0.74066 (8)	0.0254 (5)
C6	0.7580 (4)	0.17480 (16)	0.65837 (8)	0.0255 (5)
H6A	0.8739	0.1468	0.6372	0.031*
H6B	0.8220	0.1693	0.6892	0.031*
C21	0.3465 (5)	0.85174 (17)	0.54017 (8)	0.0293 (6)
H21	0.2724	0.9038	0.5248	0.035*
C20	0.2442 (5)	0.76010 (16)	0.53936 (8)	0.0256 (5)
H20	0.1010	0.7486	0.5238	0.031*
C22	0.5556 (5)	0.86812 (17)	0.56314 (8)	0.0294 (6)
H22	0.6229	0.9311	0.5629	0.035*
C15	0.3171 (4)	−0.01948 (18)	0.66364 (9)	0.0296 (6)
H15A	0.3025	−0.0514	0.6929	0.044*
H15B	0.2979	−0.0675	0.6397	0.044*
H15C	0.1955	0.0304	0.6608	0.044*
C13	0.3950 (5)	0.26533 (18)	0.78949 (8)	0.0341 (6)
H13A	0.5642	0.2548	0.7933	0.051*
H13B	0.3085	0.2106	0.8023	0.051*
H13C	0.3488	0.3251	0.8049	0.051*
C11	0.0143 (4)	0.53125 (19)	0.72999 (8)	0.0306 (6)
H11A	−0.0798	0.5614	0.7062	0.046*
H11B	0.0175	0.5738	0.7563	0.046*
H11C	−0.0557	0.4689	0.7383	0.046*
C7	0.8274 (5)	0.34770 (18)	0.51328 (8)	0.0360 (6)
H7A	0.8399	0.2771	0.5185	0.043*
H7B	0.9780	0.3782	0.5222	0.043*
C8	0.7798 (7)	0.3669 (2)	0.46500 (9)	0.0510 (9)
H8	0.8901	0.3435	0.4436	0.061*
C9	0.5962 (8)	0.4141 (2)	0.44989 (10)	0.0618 (11)
H9A	0.4824	0.4386	0.4703	0.074*
H9B	0.5768	0.4238	0.4185	0.074*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O3	0.0195 (8)	0.0234 (8)	0.0184 (8)	0.0030 (7)	−0.0004 (6)	−0.0015 (6)
O5	0.0216 (8)	0.0208 (8)	0.0301 (9)	0.0019 (7)	−0.0020 (7)	0.0024 (7)
O4	0.0251 (8)	0.0240 (8)	0.0177 (8)	−0.0017 (7)	−0.0025 (7)	0.0030 (6)
O1	0.0285 (9)	0.0194 (8)	0.0213 (8)	0.0015 (7)	0.0013 (7)	−0.0001 (6)
O10	0.0230 (9)	0.0290 (9)	0.0251 (8)	0.0002 (7)	−0.0034 (7)	0.0008 (7)
O9	0.0262 (9)	0.0274 (9)	0.0263 (8)	−0.0031 (7)	−0.0053 (7)	0.0024 (7)
O2	0.0382 (10)	0.0272 (9)	0.0176 (8)	0.0039 (8)	0.0042 (7)	−0.0010 (7)
O6	0.0239 (9)	0.0223 (9)	0.0487 (11)	0.0042 (7)	−0.0016 (9)	−0.0004 (8)
O8	0.0266 (9)	0.0419 (10)	0.0323 (9)	−0.0017 (8)	−0.0005 (8)	−0.0138 (8)
O7	0.0304 (10)	0.0493 (11)	0.0340 (10)	−0.0106 (9)	−0.0002 (9)	0.0106 (9)
N1	0.0216 (9)	0.0179 (9)	0.0183 (9)	0.0003 (8)	−0.0003 (8)	0.0018 (7)
C19	0.0223 (12)	0.0236 (12)	0.0173 (11)	−0.0004 (9)	0.0054 (10)	−0.0015 (9)
C16	0.0225 (12)	0.0232 (11)	0.0160 (10)	0.0015 (10)	0.0017 (9)	0.0001 (9)
C2	0.0217 (11)	0.0195 (11)	0.0192 (10)	−0.0003 (9)	−0.0005 (9)	0.0012 (9)
C10	0.0278 (12)	0.0215 (12)	0.0181 (11)	0.0032 (10)	−0.0014 (10)	0.0005 (9)
C1	0.0277 (12)	0.0208 (11)	0.0194 (11)	0.0013 (9)	0.0012 (10)	0.0009 (9)
C14	0.0258 (12)	0.0225 (12)	0.0205 (11)	0.0018 (10)	−0.0010 (10)	0.0001 (9)
C3	0.0180 (10)	0.0204 (11)	0.0194 (10)	0.0020 (9)	−0.0006 (9)	−0.0004 (9)
C4	0.0226 (11)	0.0201 (11)	0.0161 (10)	0.0001 (9)	−0.0033 (9)	0.0017 (8)
C17	0.0245 (11)	0.0220 (11)	0.0179 (11)	0.0004 (10)	0.0033 (10)	0.0003 (9)
C18	0.0243 (11)	0.0223 (11)	0.0167 (10)	−0.0003 (9)	0.0033 (9)	−0.0009 (9)
C23	0.0299 (12)	0.0255 (12)	0.0210 (11)	−0.0033 (10)	0.0030 (10)	−0.0033 (9)
C5	0.0225 (12)	0.0215 (11)	0.0218 (11)	0.0012 (9)	−0.0021 (9)	0.0020 (9)
C12	0.0318 (13)	0.0185 (11)	0.0259 (12)	−0.0013 (10)	0.0023 (11)	0.0021 (9)
C6	0.0209 (11)	0.0230 (11)	0.0325 (13)	0.0001 (10)	−0.0034 (11)	0.0007 (10)
C21	0.0404 (14)	0.0217 (12)	0.0259 (12)	0.0065 (11)	0.0041 (12)	0.0019 (10)
C20	0.0294 (12)	0.0260 (12)	0.0213 (11)	0.0056 (11)	0.0017 (10)	0.0013 (10)
C22	0.0428 (15)	0.0207 (12)	0.0249 (12)	−0.0051 (11)	0.0078 (11)	−0.0021 (10)
C15	0.0247 (13)	0.0280 (13)	0.0360 (14)	0.0009 (10)	0.0024 (11)	0.0018 (11)
C13	0.0537 (17)	0.0261 (13)	0.0226 (12)	−0.0088 (12)	0.0006 (12)	0.0017 (10)
C11	0.0274 (13)	0.0401 (15)	0.0243 (12)	0.0056 (12)	−0.0004 (10)	−0.0077 (11)
C7	0.0480 (16)	0.0289 (14)	0.0310 (14)	−0.0037 (12)	0.0175 (13)	−0.0068 (11)
C8	0.093 (3)	0.0335 (15)	0.0264 (15)	−0.0289 (17)	0.0232 (17)	−0.0101 (12)
C9	0.110 (3)	0.051 (2)	0.0239 (15)	−0.036 (2)	−0.0117 (17)	0.0047 (14)

Geometric parameters (Å, º) top

O3—C10	1.362 (3)	C17—C20	1.385 (3)
O3—C3	1.438 (3)	C18—C23	1.382 (3)
O5—C14	1.349 (3)	C23—H23	0.9500
O5—C6	1.444 (3)	C23—C22	1.391 (3)
O4—C4	1.438 (2)	C5—H5	1.0000
O4—C12	1.360 (3)	C5—C6	1.499 (3)
O1—C1	1.425 (3)	C12—C13	1.493 (3)
O1—C5	1.429 (3)	C6—H6A	0.9900
O10—C19	1.210 (3)	C6—H6B	0.9900
O9—C16	1.208 (3)	C21—H21	0.9500
O2—C1	1.385 (3)	C21—C20	1.393 (3)
O2—C7	1.431 (3)	C21—C22	1.390 (4)
O6—C14	1.206 (3)	C20—H20	0.9500
O8—C10	1.201 (3)	C22—H22	0.9500
O7—C12	1.200 (3)	C15—H15A	0.9800
N1—C19	1.402 (3)	C15—H15B	0.9800
N1—C16	1.404 (3)	C15—H15C	0.9800
N1—C2	1.457 (3)	C13—H13A	0.9800
C19—C18	1.483 (3)	C13—H13B	0.9800
C16—C17	1.487 (3)	C13—H13C	0.9800
C2—H2	1.0000	C11—H11A	0.9800
C2—C1	1.530 (3)	C11—H11B	0.9800
C2—C3	1.528 (3)	C11—H11C	0.9800
C10—C11	1.485 (3)	C7—H7A	0.9900
C1—H1	1.0000	C7—H7B	0.9900
C14—C15	1.484 (3)	C7—C8	1.487 (4)
C3—H3	1.0000	C8—H8	0.9500
C3—C4	1.516 (3)	C8—C9	1.310 (5)
C4—H4	1.0000	C9—H9A	0.9500
C4—C5	1.518 (3)	C9—H9B	0.9500
C17—C18	1.391 (3)

C10—O3—C3	117.72 (17)	O1—C5—H5	109.1
C14—O5—C6	115.53 (17)	O1—C5—C6	108.86 (18)
C12—O4—C4	117.20 (17)	C4—C5—H5	109.1
C1—O1—C5	112.05 (16)	C6—C5—C4	113.65 (19)
C1—O2—C7	114.16 (19)	C6—C5—H5	109.1
C19—N1—C16	111.62 (17)	O4—C12—C13	110.9 (2)
C19—N1—C2	125.71 (18)	O7—C12—O4	123.2 (2)
C16—N1—C2	122.64 (18)	O7—C12—C13	125.9 (2)
O10—C19—N1	125.1 (2)	O5—C6—C5	108.59 (18)
O10—C19—C18	128.8 (2)	O5—C6—H6A	110.0
N1—C19—C18	106.08 (19)	O5—C6—H6B	110.0
O9—C16—N1	125.3 (2)	C5—C6—H6A	110.0
O9—C16—C17	128.9 (2)	C5—C6—H6B	110.0
N1—C16—C17	105.75 (18)	H6A—C6—H6B	108.4
N1—C2—H2	107.3	C20—C21—H21	119.5
N1—C2—C1	111.67 (18)	C22—C21—H21	119.5
N1—C2—C3	111.70 (17)	C22—C21—C20	120.9 (2)
C1—C2—H2	107.3	C17—C20—C21	117.5 (2)
C3—C2—H2	107.3	C17—C20—H20	121.2
C3—C2—C1	111.17 (18)	C21—C20—H20	121.2
O3—C10—C11	110.26 (19)	C23—C22—H22	119.3
O8—C10—O3	123.2 (2)	C21—C22—C23	121.4 (2)
O8—C10—C11	126.5 (2)	C21—C22—H22	119.3
O1—C1—C2	109.66 (17)	C14—C15—H15A	109.5
O1—C1—H1	110.8	C14—C15—H15B	109.5
O2—C1—O1	107.83 (17)	C14—C15—H15C	109.5
O2—C1—C2	106.73 (18)	H15A—C15—H15B	109.5
O2—C1—H1	110.8	H15A—C15—H15C	109.5
C2—C1—H1	110.8	H15B—C15—H15C	109.5
O5—C14—C15	111.83 (19)	C12—C13—H13A	109.5
O6—C14—O5	122.5 (2)	C12—C13—H13B	109.5
O6—C14—C15	125.7 (2)	C12—C13—H13C	109.5
O3—C3—C2	107.53 (17)	H13A—C13—H13B	109.5
O3—C3—H3	110.2	H13A—C13—H13C	109.5
O3—C3—C4	108.74 (18)	H13B—C13—H13C	109.5
C2—C3—H3	110.2	C10—C11—H11A	109.5
C4—C3—C2	109.80 (17)	C10—C11—H11B	109.5
C4—C3—H3	110.2	C10—C11—H11C	109.5
O4—C4—C3	109.33 (17)	H11A—C11—H11B	109.5
O4—C4—H4	109.8	H11A—C11—H11C	109.5
O4—C4—C5	108.51 (17)	H11B—C11—H11C	109.5
C3—C4—H4	109.8	O2—C7—H7A	109.9
C3—C4—C5	109.68 (18)	O2—C7—H7B	109.9
C5—C4—H4	109.8	O2—C7—C8	108.8 (3)
C18—C17—C16	108.31 (19)	H7A—C7—H7B	108.3
C20—C17—C16	130.3 (2)	C8—C7—H7A	109.9
C20—C17—C18	121.4 (2)	C8—C7—H7B	109.9
C17—C18—C19	108.20 (19)	C7—C8—H8	117.8
C23—C18—C19	130.5 (2)	C9—C8—C7	124.5 (3)
C23—C18—C17	121.3 (2)	C9—C8—H8	117.8
C18—C23—H23	121.3	C8—C9—H9A	120.0
C18—C23—C22	117.4 (2)	C8—C9—H9B	120.0
C22—C23—H23	121.3	H9A—C9—H9B	120.0
O1—C5—C4	106.90 (17)

O3—C3—C4—O4	−68.6 (2)	C2—C3—C4—O4	173.96 (17)
O3—C3—C4—C5	172.50 (16)	C2—C3—C4—C5	55.1 (2)
O4—C4—C5—O1	178.04 (16)	C10—O3—C3—C2	−139.16 (18)
O4—C4—C5—C6	57.9 (2)	C10—O3—C3—C4	102.0 (2)
O1—C5—C6—O5	−73.7 (2)	C1—O1—C5—C4	67.7 (2)
O10—C19—C18—C17	179.9 (2)	C1—O1—C5—C6	−169.15 (18)
O10—C19—C18—C23	−0.9 (4)	C1—O2—C7—C8	−171.1 (2)
O9—C16—C17—C18	−177.5 (2)	C1—C2—C3—O3	−168.13 (17)
O9—C16—C17—C20	2.1 (4)	C1—C2—C3—C4	−50.0 (2)
O2—C7—C8—C9	1.3 (4)	C14—O5—C6—C5	173.51 (18)
N1—C19—C18—C17	−0.1 (2)	C3—O3—C10—O8	9.0 (3)
N1—C19—C18—C23	179.1 (2)	C3—O3—C10—C11	−170.29 (18)
N1—C16—C17—C18	1.9 (2)	C3—C2—C1—O1	52.8 (2)
N1—C16—C17—C20	−178.4 (2)	C3—C2—C1—O2	169.36 (17)
N1—C2—C1—O1	178.30 (17)	C3—C4—C5—O1	−62.6 (2)
N1—C2—C1—O2	−65.2 (2)	C3—C4—C5—C6	177.28 (18)
N1—C2—C3—O3	66.4 (2)	C4—O4—C12—O7	−3.4 (3)
N1—C2—C3—C4	−175.45 (18)	C4—O4—C12—C13	178.73 (19)
C19—N1—C16—O9	177.5 (2)	C4—C5—C6—O5	45.3 (3)
C19—N1—C16—C17	−2.0 (2)	C17—C18—C23—C22	−1.0 (3)
C19—N1—C2—C1	−66.5 (3)	C18—C17—C20—C21	0.7 (3)
C19—N1—C2—C3	58.7 (3)	C18—C23—C22—C21	1.4 (3)
C19—C18—C23—C22	179.9 (2)	C5—O1—C1—O2	−178.89 (17)
C16—N1—C19—O10	−178.6 (2)	C5—O1—C1—C2	−63.0 (2)
C16—N1—C19—C18	1.4 (2)	C12—O4—C4—C3	108.5 (2)
C16—N1—C2—C1	111.3 (2)	C12—O4—C4—C5	−131.9 (2)
C16—N1—C2—C3	−123.5 (2)	C6—O5—C14—O6	−9.1 (3)
C16—C17—C18—C19	−1.1 (2)	C6—O5—C14—C15	170.7 (2)
C16—C17—C18—C23	179.6 (2)	C20—C17—C18—C19	179.2 (2)
C16—C17—C20—C21	−178.9 (2)	C20—C17—C18—C23	−0.1 (3)
C2—N1—C19—O10	−0.6 (3)	C20—C21—C22—C23	−0.8 (4)
C2—N1—C19—C18	179.37 (19)	C22—C21—C20—C17	−0.3 (3)
C2—N1—C16—O9	−0.6 (3)	C7—O2—C1—O1	−68.5 (2)
C2—N1—C16—C17	179.90 (18)	C7—O2—C1—C2	173.74 (18)

Acknowledgements

The authors thank Villanova University for financial support of this work.

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