(±)-1-{8′-(tert-Butyl­diphenyl­silyloxy­meth­yl)-1′,7′-dioxaspiro­[5.5]undecan-2′-yl}uridine

Choi, K.W.; Brimble, M.A.; Groutso, T.

doi:10.1107/S1600536808006727

organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page o715

doi:10.1107/S1600536808006727

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(±)-1-{8′-(tert-Butyldiphenylsilyloxymethyl)-1′,7′-dioxaspiro[5.5]undecan-2′-yl}uridine

Ka Wai Choi,^a Margaret A. Brimble ^a ^* and Tania Groutso ^a

^aDepartment of Chemistry, Univerisity of Auckland, Private Bag 92019, Auckland, New Zealand
^*Correspondence e-mail: m.brimble@auckland.ac.nz

(Received 21 February 2008; accepted 10 March 2008; online 14 March 2008)

The crystal structure of the title compound, C₃₀H₃₈N₂O₅Si, has been investigated to establish the relative stereochemistry at the spiro ring junction and the two anomeric centres. Each of the O atoms in the tetrahydropyran rings adopts an axial position on the neighbouring ring. This bis-diaxial conformation is adopted, thus gaining maximum stablization from the anomeric effect. The silyl-protected hydroxymethyl and uracil substituents adopt equatorial positions on their associated tetrahydropyran rings, thereby minimizing unfavourable steric interactions. The dimeric (2′R*,6′R*,8′R*)- and (2′S*,6′S*,8′S*)-uridine units are connected to each other across crystallographic inversion centres via intermolecular N—H⋯O hydrogen bonds.

Related literature

For related literature, see: Mead & Zemribo (1996 ); Brimble et al. (1998 , 2004 ).

Experimental

Crystal data

C₃₀H₃₈N₂O₅Si
M_r = 534.71
Monoclinic, P 2₁ /n
a = 14.7960 (2) Å
b = 12.5092 (2) Å
c = 15.0935 (1) Å
β = 99.420 (1)°
V = 2755.93 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 293 (2) K
0.32 × 0.26 × 0.12 mm

Data collection

Siemens SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.960, T_max = 0.985
15898 measured reflections
5612 independent reflections
4327 reflections with I > 2σ(I)
R_int = 0.044

Refinement

R[F² > 2σ(F²)] = 0.052
wR(F²) = 0.111
S = 1.09
5612 reflections
343 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.34 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯O4ⁱ	0.86	2.03	2.873 (2)	166
Symmetry code: (i) -x, -y+2, -z.

Data collection: SMART (Siemens, 1995 ); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808006727/si2075sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808006727/si2075Isup2.hkl

checkCIF report

Comment top

The title uridine was prepared as a part of study to elaborate 6,6-spiroacetal scaffolds to incorporate a nucleobase at the anomeric position, thus generating a collection of novel hybrid structures. Similar syntheses of 6,6-spiroacetal based molecules in the presence of a Lewis acid and persilylated nucleophile have been reported by Mead & Zemribo (1996) and Brimble et al. (1998, 2004).

Figure 1 depicts the structure and atom numbering of the title uridine. The spiroacetal ring system adopts a conformation in which each of the O atoms (O1' and O7') adjacent to the C6' spirocentre adopts an axial position on the neighbouring ring, thus gaining maximum stabilization from the anomeric effect. The silyl-protected hydroxymethyl and uracil substituents adopt equatorial positions on their associated tetrahydropyran rings in order to minimized unfavourable steric interactions.

Figure 2 depicts molecular packing of racemic uridine units. The dimeric (2'R*,6'R*,8'R*) and (2'S*,6'S*,8'S*)-uridine units are connected to each other by the crystallographic inversion centres via intermolecular N3–H3A···O4 hydrogen bonds (Table 1).

Related literature top

For related literature, see: Mead & Zemribo (1996); Brimble et al. (1998, 2004).

Experimental top

To a suspension of uracil (6.95 mg, 61.9 µmol) in hexamethyldisilazane (0.5 ml) under an atmosphere of argon was added ammonium sulfate (2 crystals) and the mixture was heated to reflux until the white solid dissolved. After 3 h, the mixture was concentrated in vacuo to a thick yellow oil. 8-(tert-Butyldiphenylsilyloxymethyl)-2-acetoxy-1,7-dioxaspiro[5.5] undecane (18.8 mg, 38.9 µmol) in CH₂Cl₂ (1.0 ml) was transferred to the yellow oil via cannula. Freshly prepared TMSOTf solution (95.4 µL, 66.8 µmol, 0.70 mol L^-1 in CH₂Cl₂) was added dropwise. After 3 h, saturated NaHCO₃ solution (2 ml) and CH₂Cl₂ (2 ml) were added and the mixture was stirred for 15 min. The aqueous phase was extracted with CH₂Cl₂ (3 x 4 ml). The combined organic extracts were dried over MgSO₄ and concentrated in vacuo. Purification by flash chromatography using hexane–EtOAc (19:1 to 7:3) as eluent yielded the title compound (7.50 mg, 36%) as a pale-yellow powder. Recrystallization from hexane–CH₂Cl₂ afforded pale yellow needles.

HRMS (FAB): found MH⁺, 535.2633, C₃₀H₃₉N₂O₅Si requires 535.2628.

ν_max (film)/cm^-1: 3376 (N–H), 2919 (C–H), 1689 (C=O), 1668 (C=O), 1456, 1377, 1267 (C–O), 1103 (C–O), 982, 699.

δ_H (300 MHz; CDCl₃): 1.07 (9 H, s, OSiPh₂^tBu), 1.31–1.38 (1 H, m, H9'A), 1.41–1.51 (3 H, m, H3'A, H5'A and H11'A), 1.56–1.76 (5 H, m, H4'A, H5'B, H9'B, H10'A and H11'B), 1.80–1.94 (2 H, m, H3'B and H10'B), 2.07–2.16 (1 H, m, H4'B), 3.63 (1 H, dd, J_AB 10.4 and J_H1''A,8' 4.5, H1''A), 3.72 (1 H, dd, J_AB 10.4 and J_H1''B,8' 5.3, H1''B), 3.82–3.89 (1 H, m, H8'), 5.73 (1 H, d, J_5,6 8.2, H5), 5.94 (1 H, dd, J_2'ax,3'ax 11.1 and J_2'ax,3'eq 2.5, H2'_ax), 7.33–7.42 (6 H, m, Ph), 7.46 (1 H, d, J_6,5 8.2, H6), 7.70–7.76 (4 H, m, Ph), 8.17 (1 H, br s, NH).

δ_C (75 MHz; CDCl₃): 17.9 (CH₂, C4'), 18.0 (CH₂, C10'), 19.3 (C, OSiPh₂^tBu), 26.5 (CH₂, C9'), 26.8 (CH₃, OSiPh₂^tBu), 30.3 (CH₂, C3'), 34.7 (CH₂, C5'), 34.8 (CH₂, C11'), 67.0 (CH₂, C1''), 70.7 (CH, C8'), 76.8 (CH, C2'), 99.1 (C, C6'), 102.1 (CH, C5), 127.6 (CH, Ph), 129.5 (CH, Ph), 129.5 (CH, Ph), 133.8 (C, Ph), 135.7 (CH, Ph), 135.7 (CH, Ph), 140.3 (CH, C6), 149.7 (C, C2), 162.8 (C, C4).

m/z (FAB): 535 (MH⁺, 3%), 477 (M – ^tBu, 11), 457 (M – Ph, 3), 423 (C₂₆H₃₅O₃Si, 19), 239 (SiPh₂^tBu, 8), 199 (35), 197 (35), 135 (100), 105 (32), 91 (73).

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2008).

Figures top

Fig. 1. The molecular structure and atom numbering scheme of (2'S*,6'S*,8'S*)-uridine with displacement ellipsoids drawn at the 50% probability level.

Fig. 2. Molecular packing of racemic uridine units. The dimeric units of opposite chirality, (2'R*,6R'*,8'R*)- and (2'S*,6'S*,8'S*)-uridines are connected to each other by intermolecular hydrogen bonds. Dashed lines represent hydrogen bonds. Most hydrogen atoms that are not involved in hydrogen bonding, have been omitted for clarity. The origin of the unit cell is labelled as O while cell axes are labelled as a (red), b (green) and c (blue), respectively. [Symmetry code: (ii) 1/2 - x, -1/2 + y, 1/2 - z; (iii) 1/2 + x, 3/2 - y, 1/2 + z; (iv) -x + 1, -y + 1, -z + 1.]

(±)-1-{8'-(tert-Butyldiphenylsilyloxymethyl)-1',7'- dioxaspiro[5.5]undecan-2'-yl}uridine top

Crystal data top

C₃₀H₃₈N₂O₅Si	D_x = 1.289 Mg m⁻³
M_r = 534.71	Melting point: 482.4(9) K
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 14.7960 (2) Å	Cell parameters from 5612 reflections
b = 12.5092 (2) Å	θ = 1.8–26.4°
c = 15.0935 (1) Å	µ = 0.13 mm⁻¹
β = 99.420 (1)°	T = 293 K
V = 2755.93 (6) Å³	Needle, pale yellow
Z = 4	0.32 × 0.26 × 0.12 mm
F(000) = 1144

Data collection top

Siemens SMART CCD diffractometer	5612 independent reflections
Radiation source: fine-focus sealed tube	4327 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.044
area–detector ω scans	θ_max = 26.4°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→18
T_min = 0.960, T_max = 0.985	k = −15→12
15898 measured reflections	l = −18→18

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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0251P)² + 2.8069P] where P = (F_o² + 2F_c²)/3
5612 reflections	(Δ/σ)_max = 0.001
343 parameters	Δρ_max = 0.30 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₃₀H₃₈N₂O₅Si	V = 2755.93 (6) Å³
M_r = 534.71	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 14.7960 (2) Å	µ = 0.13 mm⁻¹
b = 12.5092 (2) Å	T = 293 K
c = 15.0935 (1) Å	0.32 × 0.26 × 0.12 mm
β = 99.420 (1)°

Data collection top

Siemens SMART CCD diffractometer	5612 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	4327 reflections with I > 2σ(I)
T_min = 0.960, T_max = 0.985	R_int = 0.044
15898 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.052	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.09	Δρ_max = 0.30 e Å⁻³
5612 reflections	Δρ_min = −0.34 e Å⁻³
343 parameters

Special details top

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

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 > 2σ(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
Si	0.55794 (4)	0.75101 (5)	0.10014 (4)	0.01617 (14)
O1'	0.36047 (10)	1.12404 (11)	0.28260 (9)	0.0173 (3)
O1''	0.56790 (11)	0.86029 (11)	0.16209 (10)	0.0199 (3)
O2	0.19564 (11)	0.89649 (12)	0.17326 (11)	0.0253 (4)
O4	0.00327 (12)	1.13783 (12)	0.01545 (10)	0.0267 (4)
N1	0.21693 (12)	1.07393 (14)	0.21025 (12)	0.0179 (4)
N3	0.10473 (13)	1.02092 (14)	0.09140 (12)	0.0205 (4)
H3A	0.0807	0.9715	0.0555	0.025*
C1''	0.53531 (16)	0.87555 (17)	0.24520 (14)	0.0208 (5)
H1''A	0.5834	0.8591	0.2951	0.025*
H1''B	0.4837	0.8287	0.2484	0.025*
C2	0.17425 (15)	0.98991 (17)	0.15908 (14)	0.0188 (5)
C2'	0.28987 (15)	1.04722 (17)	0.28551 (14)	0.0180 (4)
H2'A	0.3136	0.9758	0.2758	0.022*
C3'	0.25589 (15)	1.04928 (18)	0.37497 (14)	0.0204 (5)
H3'A	0.2081	0.9962	0.3752	0.025*
H3'B	0.2304	1.1190	0.3844	0.025*
C4'	0.33596 (15)	1.02537 (18)	0.44990 (14)	0.0197 (5)
H4'A	0.3162	1.0321	0.5079	0.024*
H4'B	0.3572	0.9528	0.4440	0.024*
C4	0.06939 (16)	1.12308 (18)	0.07495 (14)	0.0208 (5)
C5	0.11736 (15)	1.20464 (18)	0.13209 (14)	0.0204 (5)
H5A	0.0996	1.2758	0.1242	0.025*
C5'	0.41357 (15)	1.10398 (17)	0.44375 (14)	0.0195 (5)
H5'A	0.3947	1.1752	0.4585	0.023*
H5'B	0.4667	1.0844	0.4873	0.023*
C6'	0.43971 (15)	1.10504 (16)	0.35013 (14)	0.0174 (4)
C6	0.18739 (15)	1.17817 (17)	0.19652 (14)	0.0199 (5)
H6A	0.2169	1.2317	0.2331	0.024*
O7'	0.47639 (10)	1.00155 (11)	0.33619 (9)	0.0176 (3)
C7	0.57397 (15)	0.63171 (16)	0.17660 (13)	0.0172 (4)
C8	0.50484 (15)	0.55495 (17)	0.17660 (14)	0.0189 (5)
H8A	0.4524	0.5591	0.1334	0.023*
C8'	0.50635 (15)	0.99104 (17)	0.24987 (14)	0.0185 (5)
H8'A	0.4542	1.0045	0.2021	0.022*
C9'	0.58166 (15)	1.07096 (17)	0.24148 (15)	0.0216 (5)
H9'A	0.6008	1.0634	0.1833	0.026*
H9'B	0.6343	1.0573	0.2875	0.026*
C9	0.51259 (16)	0.47299 (17)	0.23927 (14)	0.0210 (5)
H9A	0.4657	0.4231	0.2374	0.025*
C10	0.58946 (16)	0.46522 (18)	0.30429 (15)	0.0225 (5)
H10A	0.5940	0.4110	0.3470	0.027*
C10'	0.54654 (16)	1.18395 (17)	0.25179 (14)	0.0212 (5)
H10'A	0.4993	1.2008	0.2012	0.025*
H10'B	0.5963	1.2346	0.2523	0.025*
C11'	0.50739 (15)	1.19351 (17)	0.33940 (14)	0.0193 (5)
H11'A	0.5573	1.1913	0.3898	0.023*
H11'B	0.4770	1.2621	0.3406	0.023*
C11	0.66025 (17)	0.53891 (19)	0.30570 (15)	0.0253 (5)
H11A	0.7128	0.5331	0.3486	0.030*
C12	0.65222 (16)	0.62106 (18)	0.24300 (15)	0.0233 (5)
H12A	0.6997	0.6702	0.2449	0.028*
C13	0.44029 (15)	0.74260 (17)	0.03190 (13)	0.0186 (4)
C14	0.41471 (16)	0.66001 (18)	−0.03071 (14)	0.0231 (5)
H14A	0.4575	0.6079	−0.0386	0.028*
C15	0.32729 (17)	0.65419 (19)	−0.08109 (15)	0.0265 (5)
H15A	0.3123	0.5998	−0.1229	0.032*
C16	0.26269 (17)	0.7308 (2)	−0.06812 (15)	0.0286 (6)
H16A	0.2040	0.7274	−0.1014	0.034*
C17	0.28483 (16)	0.8121 (2)	−0.00618 (16)	0.0277 (5)
H17A	0.2409	0.8623	0.0030	0.033*
C18	0.37312 (16)	0.81829 (18)	0.04222 (15)	0.0232 (5)
H18A	0.3880	0.8742	0.0826	0.028*
C19	0.63144 (17)	0.87945 (18)	−0.02047 (15)	0.0259 (5)
H19A	0.6769	0.8915	−0.0580	0.039*
H19B	0.6350	0.9350	0.0238	0.039*
H19C	0.5717	0.8798	−0.0566	0.039*
C20	0.74439 (16)	0.7706 (2)	0.08381 (16)	0.0269 (5)
H20A	0.7896	0.7806	0.0456	0.040*
H20B	0.7549	0.7037	0.1149	0.040*
H20C	0.7486	0.8278	0.1267	0.040*
C22	0.64860 (15)	0.77039 (17)	0.02668 (14)	0.0189 (5)
C23	0.64515 (17)	0.68136 (18)	−0.04386 (15)	0.0257 (5)
H23A	0.6922	0.6932	−0.0797	0.039*
H23B	0.5863	0.6818	−0.0818	0.039*
H23C	0.6548	0.6134	−0.0142	0.039*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Si	0.0173 (3)	0.0145 (3)	0.0176 (3)	−0.0002 (2)	0.0056 (2)	−0.0012 (2)
O1'	0.0150 (8)	0.0180 (8)	0.0192 (7)	−0.0014 (6)	0.0034 (6)	0.0004 (6)
O1''	0.0240 (9)	0.0181 (8)	0.0197 (7)	−0.0022 (6)	0.0095 (7)	−0.0046 (6)
O2	0.0260 (9)	0.0176 (8)	0.0308 (9)	0.0007 (7)	0.0003 (7)	−0.0006 (7)
O4	0.0294 (9)	0.0247 (9)	0.0235 (8)	0.0001 (7)	−0.0029 (7)	0.0028 (7)
O7'	0.0206 (8)	0.0159 (7)	0.0179 (7)	0.0016 (6)	0.0075 (6)	−0.0022 (6)
N1	0.0160 (9)	0.0184 (9)	0.0194 (9)	0.0006 (7)	0.0028 (7)	−0.0002 (7)
N3	0.0227 (10)	0.0192 (9)	0.0193 (9)	−0.0011 (8)	0.0027 (8)	−0.0020 (8)
C1''	0.0256 (12)	0.0199 (11)	0.0183 (10)	0.0031 (9)	0.0076 (9)	−0.0003 (9)
C2	0.0177 (11)	0.0215 (11)	0.0185 (10)	−0.0007 (9)	0.0066 (9)	−0.0003 (9)
C2'	0.0186 (11)	0.0159 (10)	0.0198 (10)	0.0005 (9)	0.0038 (9)	0.0011 (8)
C3'	0.0187 (11)	0.0202 (11)	0.0237 (11)	−0.0013 (9)	0.0076 (9)	0.0020 (9)
C4'	0.0206 (12)	0.0216 (11)	0.0181 (10)	0.0015 (9)	0.0069 (9)	0.0004 (9)
C4	0.0217 (12)	0.0226 (12)	0.0190 (11)	−0.0001 (9)	0.0062 (9)	0.0052 (9)
C5	0.0223 (12)	0.0174 (11)	0.0226 (11)	0.0021 (9)	0.0068 (9)	0.0039 (9)
C5'	0.0217 (12)	0.0193 (11)	0.0185 (10)	0.0024 (9)	0.0058 (9)	−0.0021 (9)
C6'	0.0172 (11)	0.0162 (10)	0.0187 (10)	0.0017 (9)	0.0031 (9)	−0.0016 (8)
C6	0.0208 (12)	0.0169 (11)	0.0231 (11)	−0.0017 (9)	0.0070 (9)	0.0006 (9)
C7	0.0197 (11)	0.0166 (10)	0.0166 (10)	0.0010 (9)	0.0068 (9)	−0.0025 (8)
C8	0.0159 (11)	0.0200 (11)	0.0213 (11)	0.0006 (9)	0.0049 (9)	−0.0013 (9)
C8'	0.0223 (12)	0.0183 (11)	0.0161 (10)	0.0016 (9)	0.0062 (9)	−0.0016 (8)
C9'	0.0205 (12)	0.0216 (11)	0.0243 (11)	−0.0017 (9)	0.0084 (10)	−0.0028 (9)
C9	0.0207 (12)	0.0185 (11)	0.0255 (11)	−0.0028 (9)	0.0086 (10)	−0.0009 (9)
C10	0.0297 (13)	0.0174 (11)	0.0212 (11)	0.0009 (10)	0.0068 (10)	0.0024 (9)
C10'	0.0224 (12)	0.0192 (11)	0.0226 (11)	−0.0058 (9)	0.0057 (9)	−0.0012 (9)
C11'	0.0188 (11)	0.0176 (11)	0.0220 (11)	−0.0016 (9)	0.0047 (9)	−0.0021 (9)
C11	0.0246 (13)	0.0271 (12)	0.0228 (11)	−0.0010 (10)	−0.0006 (10)	0.0015 (10)
C12	0.0248 (13)	0.0211 (11)	0.0243 (11)	−0.0040 (10)	0.0048 (10)	−0.0010 (9)
C13	0.0197 (11)	0.0191 (11)	0.0176 (10)	−0.0015 (9)	0.0046 (9)	0.0028 (9)
C14	0.0244 (13)	0.0227 (12)	0.0235 (11)	−0.0017 (10)	0.0073 (10)	−0.0022 (9)
C15	0.0304 (14)	0.0299 (13)	0.0188 (11)	−0.0105 (11)	0.0032 (10)	−0.0003 (10)
C16	0.0213 (12)	0.0390 (15)	0.0237 (11)	−0.0044 (11)	−0.0017 (10)	0.0105 (11)
C17	0.0215 (13)	0.0299 (13)	0.0311 (13)	0.0053 (10)	0.0030 (10)	0.0044 (11)
C18	0.0259 (13)	0.0207 (11)	0.0235 (11)	0.0020 (10)	0.0052 (10)	0.0021 (9)
C19	0.0322 (14)	0.0227 (12)	0.0254 (12)	−0.0005 (10)	0.0122 (10)	0.0013 (10)
C20	0.0210 (12)	0.0334 (14)	0.0275 (12)	−0.0019 (10)	0.0077 (10)	0.0027 (10)
C22	0.0186 (11)	0.0192 (11)	0.0203 (10)	−0.0003 (9)	0.0074 (9)	−0.0001 (9)
C23	0.0292 (14)	0.0229 (12)	0.0282 (12)	0.0009 (10)	0.0139 (11)	−0.0030 (10)

Geometric parameters (Å, º) top

Si—O1''	1.6491 (15)	C8'—C9'	1.518 (3)
Si—C13	1.875 (2)	C8'—H8'A	0.9800
Si—C7	1.878 (2)	C9'—C10'	1.523 (3)
Si—C22	1.891 (2)	C9'—H9'A	0.9700
O1'—C2'	1.425 (2)	C9'—H9'B	0.9700
O1'—C6'	1.442 (3)	C9—C10	1.379 (3)
O1''—C1''	1.428 (2)	C9—H9A	0.9300
O2—C2	1.220 (3)	C10—C11	1.393 (3)
O4—C4	1.229 (3)	C10—H10A	0.9300
O7'—C6'	1.433 (2)	C10'—C11'	1.533 (3)
O7'—C8'	1.449 (2)	C10'—H10'A	0.9700
N1—C6	1.380 (3)	C10'—H10'B	0.9700
N1—C2	1.393 (3)	C11'—H11'A	0.9700
N1—C2'	1.472 (3)	C11'—H11'B	0.9700
N3—C2	1.381 (3)	C11—C12	1.389 (3)
N3—C4	1.388 (3)	C11—H11A	0.9300
N3—H3A	0.8600	C12—H12A	0.9300
C1''—C8'	1.512 (3)	C13—C18	1.400 (3)
C1''—H1''A	0.9700	C13—C14	1.409 (3)
C1''—H1''B	0.9700	C14—C15	1.391 (3)
C2'—C3'	1.516 (3)	C14—H14A	0.9300
C2'—H2'A	0.9800	C15—C16	1.390 (3)
C3'—C4'	1.528 (3)	C15—H15A	0.9300
C3'—H3'A	0.9700	C16—C17	1.384 (3)
C3'—H3'B	0.9700	C16—H16A	0.9300
C4'—C5'	1.526 (3)	C17—C18	1.391 (3)
C4'—H4'A	0.9700	C17—H17A	0.9300
C4'—H4'B	0.9700	C18—H18A	0.9300
C4—C5	1.445 (3)	C19—C22	1.540 (3)
C5—C6	1.341 (3)	C19—H19A	0.9600
C5—H5A	0.9300	C19—H19B	0.9600
C5'—C6'	1.525 (3)	C19—H19C	0.9600
C5'—H5'A	0.9700	C20—C22	1.534 (3)
C5'—H5'B	0.9700	C20—H20A	0.9600
C6'—C11'	1.519 (3)	C20—H20B	0.9600
C6—H6A	0.9300	C20—H20C	0.9600
C7—C8	1.403 (3)	C22—C23	1.536 (3)
C7—C12	1.408 (3)	C23—H23A	0.9600
C8—C9	1.387 (3)	C23—H23B	0.9600
C8—H8A	0.9300	C23—H23C	0.9600

O1''—Si—C13	110.29 (9)	C9'—C8'—H8'A	109.0
O1''—Si—C7	108.65 (8)	C8'—C9'—C10'	109.60 (18)
C13—Si—C7	107.79 (10)	C8'—C9'—H9'A	109.8
O1''—Si—C22	102.72 (9)	C10'—C9'—H9'A	109.8
C13—Si—C22	111.66 (9)	C8'—C9'—H9'B	109.8
C7—Si—C22	115.59 (10)	C10'—C9'—H9'B	109.8
C2'—O1'—C6'	112.48 (15)	H9'A—C9'—H9'B	108.2
C1''—O1''—Si	126.65 (13)	C10—C9—C8	120.3 (2)
C6'—O7'—C8'	113.14 (15)	C10—C9—H9A	119.9
C6—N1—C2	121.73 (18)	C8—C9—H9A	119.9
C6—N1—C2'	120.30 (17)	C9—C10—C11	119.7 (2)
C2—N1—C2'	117.74 (17)	C9—C10—H10A	120.2
C2—N3—C4	127.16 (19)	C11—C10—H10A	120.2
C2—N3—H3A	116.4	C9'—C10'—C11'	110.13 (18)
C4—N3—H3A	116.4	C9'—C10'—H10'A	109.6
O1''—C1''—C8'	107.92 (17)	C11'—C10'—H10'A	109.6
O1''—C1''—H1''A	110.1	C9'—C10'—H10'B	109.6
C8'—C1''—H1''A	110.1	C11'—C10'—H10'B	109.6
O1''—C1''—H1''B	110.1	H10'A—C10'—H10'B	108.1
C8'—C1''—H1''B	110.1	C6'—C11'—C10'	112.58 (17)
H1''A—C1''—H1''B	108.4	C6'—C11'—H11'A	109.1
O2—C2—N3	122.6 (2)	C10'—C11'—H11'A	109.1
O2—C2—N1	123.0 (2)	C6'—C11'—H11'B	109.1
N3—C2—N1	114.42 (19)	C10'—C11'—H11'B	109.1
O1'—C2'—N1	105.77 (16)	H11'A—C11'—H11'B	107.8
O1'—C2'—C3'	111.57 (17)	C12—C11—C10	119.9 (2)
N1—C2'—C3'	112.05 (17)	C12—C11—H11A	120.0
O1'—C2'—H2'A	109.1	C10—C11—H11A	120.0
N1—C2'—H2'A	109.1	C11—C12—C7	121.6 (2)
C3'—C2'—H2'A	109.1	C11—C12—H12A	119.2
C2'—C3'—C4'	109.02 (18)	C7—C12—H12A	119.2
C2'—C3'—H3'A	109.9	C18—C13—C14	116.9 (2)
C4'—C3'—H3'A	109.9	C18—C13—Si	120.88 (17)
C2'—C3'—H3'B	109.9	C14—C13—Si	122.19 (17)
C4'—C3'—H3'B	109.9	C15—C14—C13	121.9 (2)
H3'A—C3'—H3'B	108.3	C15—C14—H14A	119.0
C5'—C4'—C3'	109.21 (17)	C13—C14—H14A	119.0
C5'—C4'—H4'A	109.8	C16—C15—C14	119.1 (2)
C3'—C4'—H4'A	109.8	C16—C15—H15A	120.5
C5'—C4'—H4'B	109.8	C14—C15—H15A	120.5
C3'—C4'—H4'B	109.8	C17—C16—C15	120.7 (2)
H4'A—C4'—H4'B	108.3	C17—C16—H16A	119.7
O4—C4—N3	120.0 (2)	C15—C16—H16A	119.7
O4—C4—C5	125.8 (2)	C16—C17—C18	119.6 (2)
N3—C4—C5	114.18 (19)	C16—C17—H17A	120.2
C6—C5—C4	120.3 (2)	C18—C17—H17A	120.2
C6—C5—H5A	119.9	C17—C18—C13	121.8 (2)
C4—C5—H5A	119.9	C17—C18—H18A	119.1
C6'—C5'—C4'	111.68 (17)	C13—C18—H18A	119.1
C6'—C5'—H5'A	109.3	C22—C19—H19A	109.5
C4'—C5'—H5'A	109.3	C22—C19—H19B	109.5
C6'—C5'—H5'B	109.3	H19A—C19—H19B	109.5
C4'—C5'—H5'B	109.3	C22—C19—H19C	109.5
H5'A—C5'—H5'B	107.9	H19A—C19—H19C	109.5
O7'—C6'—O1'	109.20 (16)	H19B—C19—H19C	109.5
O7'—C6'—C11'	111.75 (17)	C22—C20—H20A	109.5
O1'—C6'—C11'	106.17 (16)	C22—C20—H20B	109.5
O7'—C6'—C5'	106.73 (16)	H20A—C20—H20B	109.5
O1'—C6'—C5'	110.88 (17)	C22—C20—H20C	109.5
C11'—C6'—C5'	112.14 (17)	H20A—C20—H20C	109.5
C5—C6—N1	122.0 (2)	H20B—C20—H20C	109.5
C5—C6—H6A	119.0	C20—C22—C23	108.30 (19)
N1—C6—H6A	119.0	C20—C22—C19	108.97 (19)
C8—C7—C12	116.7 (2)	C23—C22—C19	109.75 (18)
C8—C7—Si	121.68 (17)	C20—C22—Si	110.46 (14)
C12—C7—Si	121.27 (16)	C23—C22—Si	111.55 (15)
C9—C8—C7	121.8 (2)	C19—C22—Si	107.78 (15)
C9—C8—H8A	119.1	C22—C23—H23A	109.5
C7—C8—H8A	119.1	C22—C23—H23B	109.5
O7'—C8'—C1''	105.03 (16)	H23A—C23—H23B	109.5
O7'—C8'—C9'	110.61 (17)	C22—C23—H23C	109.5
C1''—C8'—C9'	114.08 (19)	H23A—C23—H23C	109.5
O7'—C8'—H8'A	109.0	H23B—C23—H23C	109.5
C1''—C8'—H8'A	109.0

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O4ⁱ	0.86	2.03	2.873 (2)	166

Symmetry code: (i) −x, −y+2, −z.

Experimental details

Crystal data
Chemical formula	C₃₀H₃₈N₂O₅Si
M_r	534.71
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	14.7960 (2), 12.5092 (2), 15.0935 (1)
β (°)	99.420 (1)
V (Å³)	2755.93 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.13
Crystal size (mm)	0.32 × 0.26 × 0.12

Data collection
Diffractometer	Siemens SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.960, 0.985
No. of measured, independent and observed [I > 2σ(I)] reflections	15898, 5612, 4327
R_int	0.044
(sin θ/λ)_max (Å⁻¹)	0.625

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.052, 0.111, 1.09
No. of reflections	5612
No. of parameters	343
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.30, −0.34

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006), SHELXTL (Sheldrick, 2008) and publCIF (Westrip, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···O4ⁱ	0.86	2.031	2.873 (2)	166

Symmetry code: (i) −x, −y+2, −z.

Acknowledgements

The authors thank the New Zealand Tertiary Education Commission for the award of a Top Achiever Doctoral Scholarship (KWC).

References

Brimble, M. A., Fares, F. A. & Turner, P. (1998). J. Chem. Soc. Perkin Trans. 1, pp. 677–684. Web of Science CSD CrossRef Google Scholar
Brimble, M. A., Robinson, J. E., Choi, K. W. & Woodgate, P. D. (2004). Aust. J. Chem. 57, 665–668. Web of Science CrossRef CAS Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457. Web of Science CrossRef CAS IUCr Journals Google Scholar
Mead, K. T. & Zemribo, R. (1996). Synlett, 11, 1063–1064. CrossRef Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1995). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Westrip, S. P. (2008). publCIF. In preparation. Google Scholar

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organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

(±)-1-{8′-(tert-Butyl­di­phenyl­silyl­oxy­meth­yl)-1′,7′-dioxa­spiro­[5.5]undecan-2′-yl}uridine

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

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organic compounds

(±)-1-{8′-(tert-Butyldiphenylsilyloxymethyl)-1′,7′-dioxaspiro[5.5]undecan-2′-yl}uridine