2-Acetyl­amino-1,3,4,6-tetra-O-(tri­methyl­silyl)-2-de­oxy-α-d-gluco­pyran­ose

Cheng, Z.-D.; Cui, Y.-L.; Mao, J.-W.

doi:10.1107/S160053681301266X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 69| Part 6| June 2013| Page o917

doi:10.1107/S160053681301266X

Open

access

2-Acetylamino-1,3,4,6-tetra-O-(trimethylsilyl)-2-deoxy-α-D-glucopyranose

Zhao-Dong Cheng,^a Yan-Li Cui ^a ^* and Jian-Wei Mao ^b

^aDepartment of Chemistry, Zhejiang University, Hangzhou, Zhejiang 310027, People's Republic of China, and ^bZhejiang Provincial Key Lab for Chem. & Bio. Processing Technology of Farm Produce, Hangzhou, Zhejiang 310027, People's Republic of China
^*Correspondence e-mail: hnzzcyl@hotmail.com

(Received 26 March 2013; accepted 8 May 2013; online 18 May 2013)

The title compound, C₂₀H₄₇NO₆Si₄, was synthesized by per-O-trimethylsilylation of N-acetyl-D-glucosamine using chlorotrimethylsilane in the presence of hexamethyldisiloxane. The trimethylsilyl group and acetamido group are located on the same side of the pyran ring, showing an α-configuration glycoside. One of the trimethylsilyl groups is disordered over two orientations, with site-occupancy factors of 0.625 (9) and 0.375 (9). In the crystal, N—H⋯O hydrogen bonds link the molecules into supramolecular chains along the a-axis direction.

Related literature

For background to the title compound, see: Augé et al. (1985 ); Ronnow et al. (1994 ); Du & Gervais-Hague (2005 ); Wang et al. (2007 ); Witschi & Gervais-Hague (2010 ). For related structures, see: Odinokov et al. (2002 ); Hu et al. (2011 ). For the synthesis, see: Loganathan & Trivedi (1987 ); Jervis et al. (2010 ).

Experimental

Crystal data

C₂₀H₄₇NO₆Si₄
M_r = 509.95
Orthorhombic, P 2₁ 2₁ 2₁
a = 9.4500 (7) Å
b = 12.8824 (9) Å
c = 27.295 (3) Å
V = 3322.9 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 293 K
0.38 × 0.20 × 0.19 mm

Data collection

Agilent Xcalibur (Atlas, Gemini ultra) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.926, T_max = 0.962
9896 measured reflections
3438 independent reflections
2105 reflections with I > 2σ(I)
R_int = 0.046

Refinement

R[F² > 2σ(F²)] = 0.055
wR(F²) = 0.149
S = 1.01
3438 reflections
309 parameters
183 restraints
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O3ⁱ	0.86	2.03	2.855 (4)	160
Symmetry code: (i) $[x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+2]$ .

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009 ); software used to prepare material for publication: OLEX2.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053681301266X/zq2199sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681301266X/zq2199Isup2.hkl

checkCIF report

Comment top

Per-O-trimethylsilylated glycopyranose was an useful intermediate for the construction of oligosaccharides and glycoconjugates (Du & Gervais-Hague, 2005). Per-trimethylsilylation of unprotected sugar could increase its solubility in organic solvents, and made selective acetylation available (Witschi et al., 2010). Hu et al. have developed an one-pot α-glycoside method which also used per-O-trimethylsilylated glycosides as starting materials (Hu et al., 2011; Wang et al., 2007). Currently we have applied considerable effort towards the construction of α-glycosides (Augé et al., 1985; Ronnow et al., 1994; Jervis et al., 2010). We have synthesized the title compound and report its crystal structure herein (for related structures, see: Odinokov et al., 2002; Hu et al., 2011).

The molecular structure of the title compound is shown in Fig. 1. In the molecule, the trimethylsilyl group and acetamido group are located on the same side of the pyran ring, showing α configuration glycoside. One of the trimethylsilyl group is disordered over two orientations with site-occupancy factors of 0.625 (9) and 0.375 (9). In the crystal structure, weak intermolecular N—H···O hydrogen bonds link the molecules into supramolecular chains along the a axis in the crystal (Fig. 2).

Related literature top

For background to the title compound, see: Augé et al. (1985); Ronnow et al. (1994); Du & Gervais-Hague (2005); Wang et al. (2007); Witschi & Gervais-Hague (2010). For related structures, see: Odinokov et al. (2002); Hu et al. (2011). For the synthesis, see: Loganathan & Trivedi (1987); Jervis et al. (2010).

Experimental top

To a solution of N-acetyl-D-glucosamine (1.0 g, 4.52 mmol) in pyridine (10 mL), hexamethyldisiloxane (HMDS) (8.0 mL, 38.90 mmol) and chlorotrimethylsilane (TMSCl) (4.0 mL, 31.64 mmol) were added sequentially. The solution was stirred at 353 K under a nitrogen atmosphere for 2 hours. After cooling to rt the mixture was poured into ice-water and extracted with hexane. The organic layers were washed with brine, dried with MgSO₄, filtered, and concentrated in vacuum to furnish the crude product. The residue was purified by silica gel chromatography (petroether/ethyl acetate = 15:1) to afford the title compound. The crystal suitable for X-ray data collection was obtained by slow evaporation from a methanol solution (Jervis et al., 2010; Loganathan et al., 1987).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: OLEX2 (Dolomanov et al., 2009); software used to prepare material for publication: OLEX2 (Dolomanov et al., 2009).

Figures top

	Fig. 1. The molecular structure of the title compound with 30% probability displacement ellipsoids.
	Fig. 2. Crystal packing of the title compound showing N—H···O hydrogen bonds.

2-Acetylamino-1,3,4,6-tetra-O-(trimethylsilyl)-2-deoxy-α-D-glucopyranose top

Crystal data top

C₂₀H₄₇NO₆Si₄	F(000) = 1112
M_r = 509.95	D_x = 1.019 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1672 reflections
a = 9.4500 (7) Å	θ = 3.2–29.6°
b = 12.8824 (9) Å	µ = 0.21 mm⁻¹
c = 27.295 (3) Å	T = 293 K
V = 3322.9 (5) Å³	Needle, colourless
Z = 4	0.38 × 0.20 × 0.19 mm

Data collection top

Agilent Xcalibur (Atlas, Gemini ultra) diffractometer	3438 independent reflections
Radiation source: fine-focus sealed tube	2105 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.046
Detector resolution: 10.3592 pixels mm^-1	θ_max = 25.4°, θ_min = 3.2°
ω scans	h = −11→10
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −12→15
T_min = 0.926, T_max = 0.962	l = −30→32
9896 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.149	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0744P)² + 0.3973P] where P = (F_o² + 2F_c²)/3
3438 reflections	(Δ/σ)_max < 0.001
309 parameters	Δρ_max = 0.26 e Å⁻³
183 restraints	Δρ_min = −0.22 e Å⁻³

Crystal data top

C₂₀H₄₇NO₆Si₄	V = 3322.9 (5) Å³
M_r = 509.95	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 9.4500 (7) Å	µ = 0.21 mm⁻¹
b = 12.8824 (9) Å	T = 293 K
c = 27.295 (3) Å	0.38 × 0.20 × 0.19 mm

Data collection top

Agilent Xcalibur (Atlas, Gemini ultra) diffractometer	3438 independent reflections
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	2105 reflections with I > 2σ(I)
T_min = 0.926, T_max = 0.962	R_int = 0.046
9896 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.055	183 restraints
wR(F²) = 0.149	H-atom parameters constrained
S = 1.01	Δρ_max = 0.26 e Å⁻³
3438 reflections	Δρ_min = −0.22 e Å⁻³
309 parameters

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.

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 > 2sigma(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

	x	y	z	U_iso*/U_eq	Occ. (<1)
Si1	1.01789 (16)	0.89841 (11)	0.87673 (6)	0.0716 (4)
Si2	1.03616 (19)	0.43173 (13)	0.99519 (7)	0.0911 (6)
Si3	0.9320 (2)	0.31145 (12)	0.84396 (7)	0.0842 (5)
Si4	0.5209 (19)	0.5532 (8)	0.7757 (5)	0.1318 (13)	0.625 (9)
O1	0.7944 (3)	0.6870 (3)	0.85017 (13)	0.0726 (9)
O2	0.9849 (3)	0.7739 (2)	0.88456 (12)	0.0662 (9)
O3	0.7055 (3)	0.7511 (5)	1.00819 (18)	0.1157 (16)
O4	0.9211 (3)	0.4785 (3)	0.95578 (13)	0.0731 (10)
O5	0.9704 (4)	0.4351 (3)	0.85373 (13)	0.0751 (9)
O6	0.6763 (5)	0.5183 (4)	0.79227 (17)	0.1117 (16)
N1	0.9130 (3)	0.7012 (3)	0.97859 (14)	0.0604 (11)
H1	1.0030	0.6991	0.9831	0.072*
C1	0.8492 (5)	0.7328 (4)	0.8930 (2)	0.0646 (13)
H1A	0.7863	0.7895	0.9029	0.077*
C2	0.8562 (4)	0.6535 (4)	0.93482 (18)	0.0581 (12)
H2	0.7590	0.6320	0.9421	0.070*
C3	0.9380 (4)	0.5563 (4)	0.91906 (17)	0.0593 (12)
H3	1.0386	0.5733	0.9156	0.071*
C4	0.8818 (5)	0.5161 (4)	0.87110 (18)	0.0612 (12)
H4	0.7863	0.4886	0.8762	0.073*
C5	0.8759 (5)	0.6012 (4)	0.83238 (19)	0.0690 (14)
H5	0.9723	0.6250	0.8253	0.083*
C6	1.0050 (8)	0.9663 (5)	0.9361 (2)	0.113 (2)
H6A	0.9109	0.9591	0.9489	0.170*
H6B	1.0262	1.0386	0.9316	0.170*
H6C	1.0714	0.9366	0.9588	0.170*
C7	1.1984 (6)	0.9046 (5)	0.8523 (2)	0.0970 (19)
H7A	1.2648	0.8907	0.8781	0.146*
H7B	1.2156	0.9726	0.8392	0.146*
H7C	1.2093	0.8538	0.8269	0.146*
C8	0.8876 (7)	0.9521 (5)	0.8333 (3)	0.113 (2)
H8A	0.8682	0.9019	0.8082	0.169*
H8B	0.9251	1.0140	0.8186	0.169*
H8C	0.8017	0.9684	0.8504	0.169*
C9	0.8345 (5)	0.7478 (5)	1.0119 (2)	0.0715 (15)
C10	0.9086 (6)	0.7965 (5)	1.0546 (2)	0.0879 (17)
H10A	0.9505	0.8610	1.0446	0.132*
H10B	0.9812	0.7505	1.0662	0.132*
H10C	0.8417	0.8092	1.0804	0.132*
C11	1.0461 (9)	0.5095 (7)	1.0526 (2)	0.140 (3)
H11A	1.0800	0.5780	1.0452	0.209*
H11B	1.1097	0.4765	1.0752	0.209*
H11C	0.9537	0.5141	1.0671	0.209*
C12	1.2153 (7)	0.4319 (6)	0.9680 (3)	0.129 (3)
H12A	1.2113	0.4030	0.9356	0.194*
H12B	1.2776	0.3909	0.9880	0.194*
H12C	1.2500	0.5018	0.9663	0.194*
C13	0.9806 (11)	0.2963 (6)	1.0071 (4)	0.163 (4)
H13A	0.8920	0.2963	1.0243	0.245*
H13B	1.0511	0.2621	1.0266	0.245*
H13C	0.9698	0.2603	0.9765	0.245*
C14	1.0962 (9)	0.2396 (5)	0.8588 (3)	0.132 (3)
H14A	1.1755	0.2733	0.8436	0.198*
H14B	1.0888	0.1697	0.8468	0.198*
H14C	1.1094	0.2384	0.8937	0.198*
C15	0.7800 (8)	0.2703 (6)	0.8809 (3)	0.124 (3)
H15A	0.7923	0.2935	0.9140	0.185*
H15B	0.7732	0.1959	0.8803	0.185*
H15C	0.6950	0.2998	0.8676	0.185*
C16	0.8882 (11)	0.2878 (5)	0.7775 (3)	0.140 (3)
H16A	0.8026	0.3239	0.7692	0.210*
H16B	0.8754	0.2147	0.7721	0.210*
H16C	0.9642	0.3126	0.7573	0.210*
C17	0.8067 (7)	0.5670 (5)	0.7852 (2)	0.0922 (18)
H17A	0.7933	0.6271	0.7643	0.111*
H17B	0.8697	0.5195	0.7683	0.111*
C18A	0.4994 (16)	0.7084 (13)	0.7939 (6)	0.161 (3)	0.625 (9)
H18A	0.5411	0.7212	0.8254	0.242*	0.625 (9)
H18B	0.4013	0.7276	0.7946	0.242*	0.625 (9)
H18C	0.5476	0.7488	0.7695	0.242*	0.625 (9)
C19	0.5118 (19)	0.5859 (15)	0.7098 (5)	0.151 (3)	0.625 (9)
H19A	0.5719	0.6443	0.7032	0.226*	0.625 (9)
H19B	0.4161	0.6028	0.7012	0.226*	0.625 (9)
H19C	0.5428	0.5275	0.6908	0.226*	0.625 (9)
C20A	0.3849 (15)	0.4802 (14)	0.8078 (6)	0.170 (3)	0.625 (9)
H20A	0.3810	0.4162	0.7898	0.255*	0.625 (9)
H20B	0.2932	0.5124	0.8076	0.255*	0.625 (9)
H20C	0.4128	0.4665	0.8410	0.255*	0.625 (9)
Si4A	0.515 (3)	0.5685 (12)	0.7787 (8)	0.1318 (13)	0.375 (9)
C18	0.445 (3)	0.639 (2)	0.8231 (9)	0.161 (3)	0.375 (9)
H18D	0.4651	0.6110	0.8550	0.242*	0.375 (9)
H18E	0.3448	0.6441	0.8186	0.242*	0.375 (9)
H18F	0.4868	0.7069	0.8204	0.242*	0.375 (9)
C20	0.432 (3)	0.4260 (15)	0.7663 (10)	0.170 (3)	0.375 (9)
H20D	0.4911	0.3823	0.7465	0.255*	0.375 (9)
H20E	0.3431	0.4366	0.7502	0.255*	0.375 (9)
H20F	0.4164	0.3934	0.7975	0.255*	0.375 (9)
C19A	0.480 (3)	0.526 (3)	0.7151 (9)	0.151 (3)	0.375 (9)
H19D	0.5197	0.5750	0.6926	0.226*	0.375 (9)
H19E	0.3795	0.5215	0.7100	0.226*	0.375 (9)
H19F	0.5217	0.4589	0.7098	0.226*	0.375 (9)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Si1	0.0804 (9)	0.0542 (8)	0.0802 (9)	−0.0045 (7)	0.0034 (8)	0.0013 (8)
Si2	0.1054 (12)	0.0709 (10)	0.0970 (12)	0.0005 (9)	−0.0386 (10)	0.0153 (9)
Si3	0.1152 (12)	0.0534 (8)	0.0839 (10)	−0.0089 (9)	−0.0044 (10)	−0.0025 (8)
Si4	0.1162 (18)	0.180 (3)	0.0987 (19)	0.026 (3)	−0.0233 (15)	−0.043 (2)
O1	0.078 (2)	0.058 (2)	0.082 (2)	0.0030 (19)	−0.0269 (19)	0.001 (2)
O2	0.0583 (17)	0.0556 (19)	0.085 (2)	−0.0022 (15)	−0.0030 (16)	−0.0010 (17)
O3	0.0407 (19)	0.177 (4)	0.129 (4)	0.011 (2)	0.009 (2)	−0.036 (3)
O4	0.0725 (19)	0.068 (2)	0.079 (2)	−0.0113 (19)	−0.0134 (18)	0.0178 (19)
O5	0.087 (2)	0.0523 (18)	0.086 (2)	0.0013 (19)	−0.0010 (19)	0.0020 (18)
O6	0.130 (3)	0.094 (3)	0.111 (3)	−0.025 (3)	−0.054 (3)	0.004 (3)
N1	0.0321 (15)	0.079 (3)	0.070 (3)	0.0023 (19)	0.0012 (18)	−0.009 (2)
C1	0.054 (3)	0.059 (3)	0.080 (4)	0.006 (2)	−0.008 (2)	−0.004 (3)
C2	0.038 (2)	0.069 (3)	0.067 (3)	−0.001 (2)	−0.005 (2)	0.000 (3)
C3	0.048 (2)	0.058 (3)	0.072 (3)	−0.005 (2)	−0.005 (2)	0.010 (3)
C4	0.064 (3)	0.052 (3)	0.067 (3)	−0.008 (2)	−0.009 (2)	0.000 (3)
C5	0.076 (3)	0.057 (3)	0.074 (3)	−0.001 (3)	−0.008 (3)	0.000 (3)
C6	0.158 (6)	0.078 (4)	0.104 (5)	−0.008 (4)	0.023 (5)	−0.022 (4)
C7	0.100 (4)	0.096 (5)	0.095 (4)	−0.015 (4)	−0.003 (4)	0.010 (4)
C8	0.112 (5)	0.074 (4)	0.153 (7)	0.011 (4)	−0.012 (4)	0.027 (5)
C9	0.047 (3)	0.088 (4)	0.080 (4)	0.002 (3)	0.005 (3)	0.004 (3)
C10	0.073 (3)	0.116 (5)	0.074 (4)	0.005 (4)	0.008 (3)	−0.014 (4)
C11	0.167 (7)	0.158 (7)	0.093 (5)	0.037 (6)	−0.053 (5)	0.003 (5)
C12	0.099 (5)	0.118 (6)	0.172 (7)	0.030 (5)	−0.046 (5)	0.004 (6)
C13	0.186 (8)	0.117 (6)	0.186 (9)	−0.038 (6)	−0.079 (7)	0.073 (6)
C14	0.157 (6)	0.056 (4)	0.183 (9)	0.009 (4)	−0.006 (6)	−0.007 (5)
C15	0.148 (6)	0.089 (5)	0.134 (6)	−0.038 (5)	0.013 (5)	−0.015 (5)
C16	0.244 (10)	0.087 (5)	0.089 (5)	−0.013 (6)	−0.029 (6)	−0.012 (4)
C17	0.128 (5)	0.076 (4)	0.072 (4)	−0.005 (4)	−0.026 (4)	0.002 (3)
C18A	0.143 (5)	0.204 (7)	0.137 (6)	0.032 (5)	−0.018 (5)	−0.040 (5)
C19	0.128 (5)	0.202 (7)	0.122 (5)	0.031 (6)	−0.036 (4)	−0.032 (6)
C20A	0.145 (5)	0.218 (7)	0.148 (6)	0.008 (6)	−0.015 (5)	−0.032 (6)
Si4A	0.1162 (18)	0.180 (3)	0.0987 (19)	0.026 (3)	−0.0233 (15)	−0.043 (2)
C18	0.143 (5)	0.204 (7)	0.137 (6)	0.032 (5)	−0.018 (5)	−0.040 (5)
C20	0.145 (5)	0.218 (7)	0.148 (6)	0.008 (6)	−0.015 (5)	−0.032 (6)
C19A	0.128 (5)	0.202 (7)	0.122 (5)	0.031 (6)	−0.036 (4)	−0.032 (6)

Geometric parameters (Å, º) top

Si1—O2	1.649 (4)	C9—C10	1.498 (8)
Si1—C7	1.833 (6)	C10—H10A	0.9600
Si1—C8	1.845 (7)	C10—H10B	0.9600
Si1—C6	1.847 (6)	C10—H10C	0.9600
Si2—O4	1.644 (4)	C11—H11A	0.9600
Si2—C12	1.848 (8)	C11—H11B	0.9600
Si2—C13	1.851 (8)	C11—H11C	0.9600
Si2—C11	1.863 (7)	C12—H12A	0.9600
Si3—O5	1.655 (4)	C12—H12B	0.9600
Si3—C15	1.833 (7)	C12—H12C	0.9600
Si3—C14	1.851 (8)	C13—H13A	0.9600
Si3—C16	1.886 (7)	C13—H13B	0.9600
Si4—O6	1.60 (2)	C13—H13C	0.9600
Si4—C18	1.846 (10)	C14—H14A	0.9600
Si4—C19	1.850 (9)	C14—H14B	0.9600
Si4—C20	1.858 (10)	C14—H14C	0.9600
O1—C1	1.408 (6)	C15—H15A	0.9600
O1—C5	1.432 (6)	C15—H15B	0.9600
O2—C1	1.406 (6)	C15—H15C	0.9600
O3—C9	1.224 (5)	C16—H16A	0.9600
O4—C3	1.427 (5)	C16—H16B	0.9600
O5—C4	1.419 (6)	C16—H16C	0.9600
O6—C17	1.396 (7)	C17—H17A	0.9700
O6—Si4A	1.69 (3)	C17—H17B	0.9700
N1—C9	1.317 (6)	C18A—Si4A	1.856 (10)
N1—C2	1.447 (6)	C18A—H18A	0.9600
N1—H1	0.8600	C18A—H18B	0.9600
C1—C2	1.532 (7)	C18A—H18C	0.9600
C1—H1A	0.9800	C19—H19A	0.9600
C2—C3	1.533 (6)	C19—H19B	0.9600
C2—H2	0.9800	C19—H19C	0.9600
C3—C4	1.505 (6)	C20A—Si4A	1.856 (10)
C3—H3	0.9800	C20A—H20A	0.9600
C4—C5	1.525 (7)	C20A—H20B	0.9600
C4—H4	0.9800	C20A—H20C	0.9600
C5—C17	1.511 (7)	Si4A—C19A	1.851 (10)
C5—H5	0.9800	C18—H18D	0.9600
C6—H6A	0.9600	C18—H18E	0.9600
C6—H6B	0.9600	C18—H18F	0.9600
C6—H6C	0.9600	C20—H20D	0.9600
C7—H7A	0.9600	C20—H20E	0.9600
C7—H7B	0.9600	C20—H20F	0.9600
C7—H7C	0.9600	C19A—H19D	0.9600
C8—H8A	0.9600	C19A—H19E	0.9600
C8—H8B	0.9600	C19A—H19F	0.9600
C8—H8C	0.9600

O2—Si1—C7	105.4 (3)	Si1—C8—H8C	109.5
O2—Si1—C8	108.8 (3)	H8A—C8—H8C	109.5
C7—Si1—C8	111.8 (3)	H8B—C8—H8C	109.5
O2—Si1—C6	109.6 (3)	O3—C9—N1	121.3 (5)
C7—Si1—C6	111.1 (3)	O3—C9—C10	121.0 (5)
C8—Si1—C6	110.1 (4)	N1—C9—C10	117.7 (4)
O4—Si2—C12	110.0 (3)	C9—C10—H10A	109.5
O4—Si2—C13	105.8 (3)	C9—C10—H10B	109.5
C12—Si2—C13	109.4 (4)	H10A—C10—H10B	109.5
O4—Si2—C11	112.8 (3)	C9—C10—H10C	109.5
C12—Si2—C11	106.9 (4)	H10A—C10—H10C	109.5
C13—Si2—C11	111.9 (5)	H10B—C10—H10C	109.5
O5—Si3—C15	111.2 (3)	Si2—C11—H11A	109.5
O5—Si3—C14	105.2 (3)	Si2—C11—H11B	109.5
C15—Si3—C14	113.1 (4)	H11A—C11—H11B	109.5
O5—Si3—C16	111.0 (3)	Si2—C11—H11C	109.5
C15—Si3—C16	108.0 (4)	H11A—C11—H11C	109.5
C14—Si3—C16	108.3 (4)	H11B—C11—H11C	109.5
O6—Si4—C18	109.0 (12)	Si2—C12—H12A	109.5
O6—Si4—C19	112.4 (9)	Si2—C12—H12B	109.5
C18—Si4—C19	121.8 (15)	H12A—C12—H12B	109.5
O6—Si4—C20	101.9 (11)	Si2—C12—H12C	109.5
C18—Si4—C20	116.8 (15)	H12A—C12—H12C	109.5
C19—Si4—C20	92.6 (13)	H12B—C12—H12C	109.5
C1—O1—C5	114.0 (3)	Si2—C13—H13A	109.5
C1—O2—Si1	124.1 (3)	Si2—C13—H13B	109.5
C3—O4—Si2	130.0 (3)	H13A—C13—H13B	109.5
C4—O5—Si3	129.2 (3)	Si2—C13—H13C	109.5
C17—O6—Si4	130.2 (5)	H13A—C13—H13C	109.5
C17—O6—Si4A	126.2 (7)	H13B—C13—H13C	109.5
C9—N1—C2	123.7 (4)	Si3—C14—H14A	109.5
C9—N1—H1	118.2	Si3—C14—H14B	109.5
C2—N1—H1	118.2	H14A—C14—H14B	109.5
O2—C1—O1	110.9 (4)	Si3—C14—H14C	109.5
O2—C1—C2	109.5 (3)	H14A—C14—H14C	109.5
O1—C1—C2	110.8 (4)	H14B—C14—H14C	109.5
O2—C1—H1A	108.5	Si3—C15—H15A	109.5
O1—C1—H1A	108.5	Si3—C15—H15B	109.5
C2—C1—H1A	108.5	H15A—C15—H15B	109.5
N1—C2—C1	110.3 (4)	Si3—C15—H15C	109.5
N1—C2—C3	113.1 (3)	H15A—C15—H15C	109.5
C1—C2—C3	110.9 (4)	H15B—C15—H15C	109.5
N1—C2—H2	107.4	Si3—C16—H16A	109.5
C1—C2—H2	107.4	Si3—C16—H16B	109.5
C3—C2—H2	107.4	H16A—C16—H16B	109.5
O4—C3—C4	109.2 (4)	Si3—C16—H16C	109.5
O4—C3—C2	108.7 (4)	H16A—C16—H16C	109.5
C4—C3—C2	110.3 (4)	H16B—C16—H16C	109.5
O4—C3—H3	109.5	O6—C17—C5	113.3 (5)
C4—C3—H3	109.5	O6—C17—H17A	108.9
C2—C3—H3	109.5	C5—C17—H17A	108.9
O5—C4—C3	109.6 (4)	O6—C17—H17B	108.9
O5—C4—C5	108.6 (4)	C5—C17—H17B	108.9
C3—C4—C5	111.6 (4)	H17A—C17—H17B	107.7
O5—C4—H4	109.0	Si4A—C18A—H18A	109.5
C3—C4—H4	109.0	Si4A—C18A—H18B	109.5
C5—C4—H4	109.0	H18A—C18A—H18B	109.5
O1—C5—C17	106.4 (4)	Si4A—C18A—H18C	109.5
O1—C5—C4	109.9 (4)	H18A—C18A—H18C	109.5
C17—C5—C4	113.4 (4)	H18B—C18A—H18C	109.5
O1—C5—H5	109.0	Si4A—C20A—H20A	109.5
C17—C5—H5	109.0	Si4A—C20A—H20B	109.5
C4—C5—H5	109.0	H20A—C20A—H20B	109.5
Si1—C6—H6A	109.5	Si4A—C20A—H20C	109.5
Si1—C6—H6B	109.5	H20A—C20A—H20C	109.5
H6A—C6—H6B	109.5	H20B—C20A—H20C	109.5
Si1—C6—H6C	109.5	O6—Si4A—C19A	104.8 (14)
H6A—C6—H6C	109.5	O6—Si4A—C18A	113.3 (14)
H6B—C6—H6C	109.5	C19A—Si4A—C18A	118.8 (17)
Si1—C7—H7A	109.5	O6—Si4A—C20A	105.7 (12)
Si1—C7—H7B	109.5	C19A—Si4A—C20A	95.6 (16)
H7A—C7—H7B	109.5	C18A—Si4A—C20A	116.5 (14)
Si1—C7—H7C	109.5	Si4A—C19A—H19D	109.5
H7A—C7—H7C	109.5	Si4A—C19A—H19E	109.5
H7B—C7—H7C	109.5	H19D—C19A—H19E	109.5
Si1—C8—H8A	109.5	Si4A—C19A—H19F	109.5
Si1—C8—H8B	109.5	H19D—C19A—H19F	109.5
H8A—C8—H8B	109.5	H19E—C19A—H19F	109.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3ⁱ	0.86	2.03	2.855 (4)	160

Symmetry code: (i) x+1/2, −y+3/2, −z+2.

Experimental details

Crystal data
Chemical formula	C₂₀H₄₇NO₆Si₄
M_r	509.95
Crystal system, space group	Orthorhombic, P2₁2₁2₁
Temperature (K)	293
a, b, c (Å)	9.4500 (7), 12.8824 (9), 27.295 (3)
V (Å³)	3322.9 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.21
Crystal size (mm)	0.38 × 0.20 × 0.19

Data collection
Diffractometer	Agilent Xcalibur (Atlas, Gemini ultra) diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.926, 0.962
No. of measured, independent and observed [I > 2σ(I)] reflections	9896, 3438, 2105
R_int	0.046
(sin θ/λ)_max (Å⁻¹)	0.602

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.055, 0.149, 1.01
No. of reflections	3438
No. of parameters	309
No. of restraints	183
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.22

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), OLEX2 (Dolomanov et al., 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O3ⁱ	0.86	2.03	2.855 (4)	160

Symmetry code: (i) x+1/2, −y+3/2, −z+2.

Acknowledgements

This work was supported financially by the National Science Foundation of China (No. 30870553) and the Key International S&T Cooperation Project, China (No. 2010DFA34370).

References

Agilent (2011). CrysAlis PRO, Agilent Technologies, Yarnton, England. Google Scholar
Augé, C., David, S., Gautheron, C. & Veyrières, A. (1985). Tetrahedron Lett. 26, 2439–2440. Google Scholar
Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K. & Puschmann, H. (2009). J. Appl. Cryst. 42, 339–341. Web of Science CrossRef CAS IUCr Journals Google Scholar
Du, W. & Gervais-Hague, J. (2005). Org. Lett. 7, 2063–2065. Web of Science CrossRef PubMed CAS Google Scholar
Hu, Y.-P., Lin, S.-Y., Huang, C.-Y., Zulueta, M. M., Liu, J.-Y., Chang, W. & Hung, S.-C. (2011). Nat. Chem. 3, 557–563. Web of Science CrossRef CAS PubMed Google Scholar
Jervis, P. J., Veerapen, N., Bricard, G., Cox, L. R., Porcelli, S. A. & Besra, G. S. (2010). Bioorg. Med. Chem. Lett. 20, 3475–3478. Web of Science CrossRef CAS PubMed Google Scholar
Loganathan, D. & Trivedi, G. K. (1987). Carbohydr. Res. 162, 117–125. CrossRef CAS Web of Science Google Scholar
Odinokov, V. N., Savchenko, R. G., Nazmeeva, S. R., Galyautdinov, I. V. & Khalilov, L. M. (2002). Russ. Chem. Bull. 51, 1937–1939. Web of Science CrossRef CAS Google Scholar
Ronnow, T. E. C. L., Meldal, M. & Bock, K. (1994). Carbohydr. Res. 260, 323–328. CAS PubMed Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, C.-C., Lee, J.-C., Luo, S.-Y., Kulkarni, S.-S., Huang, Y.-W., Lee, C.-C., Chang, K.-L. & Hung, S.-C. (2007). Nature, 446, 896–899. Web of Science CrossRef PubMed CAS Google Scholar
Witschi, M. A. & Gervais-Hague, J. (2010). Org. Lett. 12, 4312–4315. Web of Science CrossRef CAS PubMed Google Scholar