2,3,4-Tri-O-acetyl-β-l-arabinopyranosyl trichloro­acetimidate

Sun, Z.-L.

doi:10.1107/S1600536811002005

organic compounds

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ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o454

doi:10.1107/S1600536811002005

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2,3,4-Tri-O-acetyl-β-L-arabinopyranosyl trichloroacetimidate

Zu-Li Sun ^a ^*

^aScience and Engineering College of Chemistry and Biology, Yantai University, Yantai 264005, People's Republic of China
^*Correspondence e-mail: zulisun10@126.com

(Received 9 January 2011; accepted 13 January 2011; online 22 January 2011)

In the title compound, C₁₃H₁₆Cl₃NO₈, the trichloroacetimidate group is located in an axial postion on the anomeric carbon of the sugar ring.

Related literature

For applications of glycosyl trichloroacetimidate in glycosyl bond formation, see: Schmidt & Zhu (2008 ). For the preparation of the title compound, see: Schmidt & Stumpp (1983 ).

Experimental

Crystal data

C₁₃H₁₆Cl₃NO₈
M_r = 420.62
Monoclinic, C 2
a = 21.384 (5) Å
b = 6.7994 (16) Å
c = 13.096 (3) Å
β = 96.796 (3)°
V = 1890.7 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.52 mm⁻¹
T = 298 K
0.49 × 0.24 × 0.08 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ) T_min = 0.784, T_max = 0.959
4972 measured reflections
3239 independent reflections
2933 reflections with I > 2σ(I)
R_int = 0.021

Refinement

R[F² > 2σ(F²)] = 0.037
wR(F²) = 0.087
S = 1.06
3239 reflections
226 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.17 e Å⁻³
Absolute structure: Flack (1983 ), 1334 Friedel pairs
Flack parameter: 0.04 (6)

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811002005/jh2255sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811002005/jh2255Isup2.hkl

checkCIF report

Comment top

The title compound, a very useful glycosyl intermediate in glycosyl bond formation, was prepared from L-arabinose according to literature (Schmidt et al., 1983) and its structure was further characterized by X-ray crystallographic techniques. The structure of 2,3,4-tri-O-acetyl-β-L-arabinopyranosyl trichloroacetimidate has monoclinic (C2) symmetry. The structure reveals that the trichloroacetimidate group is located at axial postion on anomeric carbon of sugar ring, as shown in Fig. 1. There is hydrogen bond interaction between N (1) and Cl (2) on the trichloroacetimidate group [N(1)···Cl(2) 3.009 (3) Å and N(1)—H(1)···Cl(2) 113.5 °].

Related literature top

For applications of glycosyl trichloroacetimidate in glycosyl bond formation, see: Schmidt et al. (2008). For the preparation of the title compound, see: Schmidt et al. (1983).

Experimental top

The title compound was prepared from L-arabinose by the following three steps: i) acetylation with Ac₂O in pyridine; ii) selective removal of acetyl group on anomeric carbon by ammonia methanol solution; iii) trichloroacetimidate formation with Cl₃CN/DBU in dichloromethane. Colorless single crystals were grown from a solution of petroleum ether/ethyl acetate (2:1).

Computing details top

Data collection: SMART (Bruker, 2003); cell refinement: SAINT (Bruker, 2003); data reduction: SAINT (Bruker, 2003); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. Elipsoid plot.

2,3,4-tri-O-acetyl-β-L-arabinopyranosyl trichloroacetimidate top

Crystal data top

C₁₃H₁₆Cl₃NO₈	F(000) = 864
M_r = 420.62	D_x = 1.478 Mg m⁻³
Monoclinic, C2	Mo Kα radiation, λ = 0.71073 Å
a = 21.384 (5) Å	Cell parameters from 2245 reflections
b = 6.7994 (16) Å	θ = 2.6–23.4°
c = 13.096 (3) Å	µ = 0.52 mm⁻¹
β = 96.796 (3)°	T = 298 K
V = 1890.7 (8) Å³	Plan, colourless
Z = 4	0.49 × 0.24 × 0.08 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	3239 independent reflections
Radiation source: fine-focus sealed tube	2933 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.021
ϕ and ω scans	θ_max = 25.5°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −25→21
T_min = 0.784, T_max = 0.959	k = −8→6
4972 measured reflections	l = −12→15

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.087	w = 1/[σ²(F_o²) + (0.0276P)² + 0.9525P] where P = (F_o² + 2F_c²)/3
S = 1.06	(Δ/σ)_max = 0.006
3239 reflections	Δρ_max = 0.23 e Å⁻³
226 parameters	Δρ_min = −0.17 e Å⁻³
1 restraint	Absolute structure: Flack (1983), 1334 Friedel pairs
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.04 (6)

Crystal data top

C₁₃H₁₆Cl₃NO₈	V = 1890.7 (8) Å³
M_r = 420.62	Z = 4
Monoclinic, C2	Mo Kα radiation
a = 21.384 (5) Å	µ = 0.52 mm⁻¹
b = 6.7994 (16) Å	T = 298 K
c = 13.096 (3) Å	0.49 × 0.24 × 0.08 mm
β = 96.796 (3)°

Data collection top

Bruker SMART CCD area-detector diffractometer	3239 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2003)	2933 reflections with I > 2σ(I)
T_min = 0.784, T_max = 0.959	R_int = 0.021
4972 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.037	H-atom parameters constrained
wR(F²) = 0.087	Δρ_max = 0.23 e Å⁻³
S = 1.06	Δρ_min = −0.17 e Å⁻³
3239 reflections	Absolute structure: Flack (1983), 1334 Friedel pairs
226 parameters	Absolute structure parameter: 0.04 (6)
1 restraint

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

	x	y	z	U_iso*/U_eq	Occ. (<1)
C2	0.61191 (15)	0.4264 (8)	0.4040 (2)	0.0721 (11)
C3	0.71252 (13)	0.5071 (4)	0.3556 (2)	0.0431 (7)
H3A	0.6937	0.6380	0.3448	0.052*
C4	0.77597 (14)	0.5222 (4)	0.4187 (2)	0.0479 (7)
H4A	0.8017	0.6154	0.3862	0.057*
H4B	0.7704	0.5729	0.4863	0.057*
C5	0.81676 (12)	0.2479 (4)	0.33786 (19)	0.0385 (6)
H5A	0.8369	0.1197	0.3519	0.046*
C6	0.75450 (12)	0.2193 (4)	0.27061 (18)	0.0354 (6)
H6A	0.7285	0.1266	0.3044	0.042*
C7	0.71942 (11)	0.4112 (4)	0.25338 (17)	0.0354 (5)
H7A	0.7423	0.4991	0.2115	0.042*
C8	0.91695 (12)	0.3220 (4)	0.2839 (2)	0.0449 (7)
C9	0.94598 (13)	0.4576 (5)	0.2087 (2)	0.0518 (7)
C10	0.77615 (13)	−0.0517 (4)	0.1675 (2)	0.0453 (7)
C11	0.62909 (13)	0.5066 (5)	0.1420 (2)	0.0461 (7)
C12	0.56681 (14)	0.4375 (7)	0.0926 (3)	0.0725 (10)
H12A	0.5464	0.5418	0.0519	0.109*
H12B	0.5412	0.3995	0.1447	0.109*
H12C	0.5726	0.3267	0.0493	0.109*
C13	0.78124 (19)	−0.1138 (5)	0.0615 (3)	0.0723 (10)
H13A	0.7903	−0.2520	0.0604	0.109*
H13B	0.8145	−0.0419	0.0353	0.109*
H13C	0.7422	−0.0881	0.0195	0.109*
Cl1	0.93304 (4)	0.70622 (13)	0.24083 (7)	0.0688 (3)
Cl2	1.02723 (4)	0.41909 (16)	0.21284 (8)	0.0838 (3)
Cl3	0.90994 (5)	0.40977 (19)	0.08308 (6)	0.0833 (3)
O1	0.58775 (12)	0.5583 (6)	0.3561 (2)	0.0997 (11)
O2	0.76398 (9)	0.1433 (2)	0.17167 (13)	0.0429 (4)
O3	0.78190 (11)	−0.1520 (3)	0.24214 (18)	0.0617 (6)
O4	0.85537 (8)	0.3662 (3)	0.27922 (14)	0.0441 (4)
O5	0.67371 (8)	0.3848 (3)	0.41230 (13)	0.0521 (5)
O6	0.65015 (10)	0.6661 (3)	0.13335 (17)	0.0622 (6)
O7	0.65915 (8)	0.3634 (3)	0.19901 (13)	0.0436 (5)
O8	0.80828 (8)	0.3379 (3)	0.43005 (13)	0.0445 (5)
N1	0.94316 (12)	0.1918 (5)	0.3390 (2)	0.0720 (9)
H1	0.9834	0.1736	0.3329	0.108*
C1	0.57884 (18)	0.2786 (11)	0.4638 (3)	0.125 (2)
H1A	0.5975	0.2786	0.5342	0.187*	0.50
H1B	0.5828	0.1502	0.4349	0.187*	0.50
H1C	0.5351	0.3126	0.4607	0.187*	0.50
H1'1	0.5638	0.3421	0.5217	0.187*	0.50
H1'2	0.6077	0.1757	0.4877	0.187*	0.50
H1'3	0.5439	0.2236	0.4204	0.187*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C2	0.0401 (16)	0.130 (4)	0.0470 (16)	0.021 (2)	0.0094 (13)	0.009 (2)
C3	0.0419 (15)	0.0449 (17)	0.0431 (14)	0.0097 (12)	0.0079 (11)	0.0031 (12)
C4	0.0467 (17)	0.0527 (19)	0.0437 (15)	0.0000 (14)	0.0027 (12)	−0.0069 (13)
C5	0.0312 (13)	0.0394 (16)	0.0447 (15)	0.0055 (11)	0.0040 (11)	0.0105 (12)
C6	0.0375 (13)	0.0336 (14)	0.0359 (13)	0.0016 (11)	0.0078 (10)	0.0053 (11)
C7	0.0317 (12)	0.0351 (14)	0.0394 (12)	0.0002 (12)	0.0043 (10)	0.0052 (12)
C8	0.0304 (13)	0.0492 (18)	0.0543 (16)	0.0029 (13)	0.0022 (12)	0.0009 (14)
C9	0.0375 (15)	0.0553 (19)	0.0639 (17)	0.0045 (14)	0.0122 (13)	0.0024 (15)
C10	0.0404 (14)	0.0346 (16)	0.0615 (17)	−0.0002 (12)	0.0087 (13)	−0.0024 (14)
C11	0.0378 (15)	0.062 (2)	0.0380 (14)	0.0087 (14)	0.0025 (11)	0.0069 (13)
C12	0.0437 (17)	0.095 (3)	0.074 (2)	0.0004 (19)	−0.0150 (15)	0.017 (2)
C13	0.096 (3)	0.048 (2)	0.076 (2)	0.0055 (19)	0.0225 (19)	−0.0130 (18)
Cl1	0.0594 (5)	0.0493 (5)	0.1014 (7)	0.0004 (4)	0.0246 (4)	0.0029 (5)
Cl2	0.0401 (4)	0.0873 (7)	0.1296 (8)	0.0112 (4)	0.0332 (5)	0.0213 (6)
Cl3	0.0909 (7)	0.1090 (8)	0.0525 (4)	−0.0057 (6)	0.0185 (4)	0.0003 (5)
O1	0.0543 (15)	0.161 (3)	0.0849 (18)	0.0531 (18)	0.0137 (13)	0.026 (2)
O2	0.0549 (12)	0.0344 (11)	0.0407 (10)	0.0050 (8)	0.0117 (8)	0.0045 (8)
O3	0.0771 (15)	0.0365 (12)	0.0708 (14)	0.0036 (11)	0.0056 (11)	0.0099 (11)
O4	0.0290 (9)	0.0485 (12)	0.0558 (10)	0.0062 (8)	0.0093 (7)	0.0142 (9)
O5	0.0339 (9)	0.0780 (15)	0.0454 (10)	0.0122 (10)	0.0086 (8)	0.0120 (11)
O6	0.0526 (13)	0.0589 (16)	0.0721 (14)	0.0066 (11)	−0.0053 (10)	0.0246 (12)
O7	0.0336 (9)	0.0472 (12)	0.0479 (10)	0.0013 (9)	−0.0038 (7)	0.0051 (9)
O8	0.0382 (10)	0.0553 (12)	0.0389 (9)	0.0044 (9)	0.0000 (8)	0.0068 (9)
N1	0.0384 (14)	0.083 (2)	0.095 (2)	0.0141 (15)	0.0109 (13)	0.0363 (19)
C1	0.045 (2)	0.251 (7)	0.080 (3)	−0.011 (3)	0.0175 (19)	0.045 (4)

Geometric parameters (Å, º) top

C2—O1	1.178 (5)	C9—Cl2	1.752 (3)
C2—O5	1.343 (4)	C9—Cl3	1.763 (3)
C2—C1	1.502 (6)	C9—Cl1	1.771 (3)
C3—O5	1.442 (3)	C10—O3	1.187 (3)
C3—C4	1.506 (4)	C10—O2	1.353 (3)
C3—C7	1.512 (4)	C10—C13	1.467 (4)
C3—H3A	0.9800	C11—O6	1.185 (4)
C4—O8	1.430 (3)	C11—O7	1.344 (3)
C4—H4A	0.9700	C11—C12	1.486 (4)
C4—H4B	0.9700	C12—H12A	0.9600
C5—O8	1.385 (3)	C12—H12B	0.9600
C5—O4	1.438 (3)	C12—H12C	0.9600
C5—C6	1.519 (3)	C13—H13A	0.9600
C5—H5A	0.9800	C13—H13B	0.9600
C6—O2	1.432 (3)	C13—H13C	0.9600
C6—C7	1.508 (4)	N1—H1	0.8820
C6—H6A	0.9800	C1—H1A	0.9600
C7—O7	1.434 (3)	C1—H1B	0.9600
C7—H7A	0.9800	C1—H1C	0.9600
C8—N1	1.234 (4)	C1—H1'1	0.9600
C8—O4	1.345 (3)	C1—H1'2	0.9600
C8—C9	1.533 (4)	C1—H1'3	0.9600

O1—C2—O5	124.7 (4)	O2—C10—C13	110.9 (3)
O1—C2—C1	125.7 (3)	O6—C11—O7	123.6 (3)
O5—C2—C1	109.6 (4)	O6—C11—C12	125.4 (3)
O5—C3—C4	107.0 (2)	O7—C11—C12	111.0 (3)
O5—C3—C7	109.2 (2)	C11—C12—H12A	109.5
C4—C3—C7	109.8 (2)	C11—C12—H12B	109.5
O5—C3—H3A	110.2	H12A—C12—H12B	109.5
C4—C3—H3A	110.2	C11—C12—H12C	109.5
C7—C3—H3A	110.2	H12A—C12—H12C	109.5
O8—C4—C3	113.0 (2)	H12B—C12—H12C	109.5
O8—C4—H4A	109.0	C10—C13—H13A	109.5
C3—C4—H4A	109.0	C10—C13—H13B	109.5
O8—C4—H4B	109.0	H13A—C13—H13B	109.5
C3—C4—H4B	109.0	C10—C13—H13C	109.5
H4A—C4—H4B	107.8	H13A—C13—H13C	109.5
O8—C5—O4	111.1 (2)	H13B—C13—H13C	109.5
O8—C5—C6	111.5 (2)	C10—O2—C6	116.1 (2)
O4—C5—C6	106.32 (19)	C8—O4—C5	118.1 (2)
O8—C5—H5A	109.3	C2—O5—C3	117.2 (3)
O4—C5—H5A	109.3	C11—O7—C7	117.0 (2)
C6—C5—H5A	109.3	C5—O8—C4	114.1 (2)
O2—C6—C7	107.34 (19)	C8—N1—H1	115.3
O2—C6—C5	111.3 (2)	C2—C1—H1A	109.5
C7—C6—C5	111.2 (2)	C2—C1—H1B	109.5
O2—C6—H6A	109.0	H1A—C1—H1B	109.5
C7—C6—H6A	109.0	C2—C1—H1C	109.5
C5—C6—H6A	109.0	H1A—C1—H1C	109.5
O7—C7—C6	106.3 (2)	H1B—C1—H1C	109.5
O7—C7—C3	111.17 (19)	C2—C1—H1'1	109.5
C6—C7—C3	109.9 (2)	H1A—C1—H1'1	51.8
O7—C7—H7A	109.8	H1B—C1—H1'1	140.8
C6—C7—H7A	109.8	H1C—C1—H1'1	60.7
C3—C7—H7A	109.8	C2—C1—H1'2	109.5
N1—C8—O4	124.2 (3)	H1A—C1—H1'2	60.7
N1—C8—C9	128.1 (3)	H1B—C1—H1'2	51.8
O4—C8—C9	107.8 (2)	H1C—C1—H1'2	140.8
C8—C9—Cl2	111.5 (2)	H1'1—C1—H1'2	109.5
C8—C9—Cl3	108.8 (2)	C2—C1—H1'3	109.5
Cl2—C9—Cl3	108.89 (17)	H1A—C1—H1'3	140.8
C8—C9—Cl1	109.6 (2)	H1B—C1—H1'3	60.7
Cl2—C9—Cl1	108.52 (17)	H1C—C1—H1'3	51.8
Cl3—C9—Cl1	109.53 (17)	H1'1—C1—H1'3	109.5
O3—C10—O2	122.1 (3)	H1'2—C1—H1'3	109.5
O3—C10—C13	127.0 (3)

O5—C3—C4—O8	64.9 (3)	O3—C10—O2—C6	−3.8 (4)
C7—C3—C4—O8	−53.5 (3)	C13—C10—O2—C6	176.7 (2)
O8—C5—C6—O2	174.5 (2)	C7—C6—O2—C10	−159.8 (2)
O4—C5—C6—O2	53.3 (3)	C5—C6—O2—C10	78.3 (3)
O8—C5—C6—C7	54.9 (3)	N1—C8—O4—C5	−3.4 (4)
O4—C5—C6—C7	−66.4 (2)	C9—C8—O4—C5	175.5 (2)
O2—C6—C7—O7	64.1 (2)	O8—C5—O4—C8	98.2 (3)
C5—C6—C7—O7	−173.92 (18)	C6—C5—O4—C8	−140.3 (2)
O2—C6—C7—C3	−175.5 (2)	O1—C2—O5—C3	−2.1 (5)
C5—C6—C7—C3	−53.6 (3)	C1—C2—O5—C3	177.3 (3)
O5—C3—C7—O7	52.8 (3)	C4—C3—O5—C2	146.6 (3)
C4—C3—C7—O7	169.9 (2)	C7—C3—O5—C2	−94.6 (3)
O5—C3—C7—C6	−64.5 (3)	O6—C11—O7—C7	1.3 (4)
C4—C3—C7—C6	52.5 (3)	C12—C11—O7—C7	−178.5 (2)
N1—C8—C9—Cl2	−3.6 (4)	C6—C7—O7—C11	−155.7 (2)
O4—C8—C9—Cl2	177.5 (2)	C3—C7—O7—C11	84.8 (3)
N1—C8—C9—Cl3	116.5 (3)	O4—C5—O8—C4	62.6 (3)
O4—C8—C9—Cl3	−62.4 (3)	C6—C5—O8—C4	−55.8 (3)
N1—C8—C9—Cl1	−123.8 (3)	C3—C4—O8—C5	56.4 (3)
O4—C8—C9—Cl1	57.3 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2	0.88	2.55	3.009 (3)	114

Experimental details

Crystal data
Chemical formula	C₁₃H₁₆Cl₃NO₈
M_r	420.62
Crystal system, space group	Monoclinic, C2
Temperature (K)	298
a, b, c (Å)	21.384 (5), 6.7994 (16), 13.096 (3)
β (°)	96.796 (3)
V (Å³)	1890.7 (8)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.52
Crystal size (mm)	0.49 × 0.24 × 0.08

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2003)
T_min, T_max	0.784, 0.959
No. of measured, independent and observed [I > 2σ(I)] reflections	4972, 3239, 2933
R_int	0.021
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.037, 0.087, 1.06
No. of reflections	3239
No. of parameters	226
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.17
Absolute structure	Flack (1983), 1334 Friedel pairs
Absolute structure parameter	0.04 (6)

Computer programs: SMART (Bruker, 2003), SAINT (Bruker, 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2	0.88	2.55	3.009 (3)	114

Acknowledgements

This work was supported by a grant from the National High Technology Research and Development Program of China (863 Program) (No. 2007AA03A229)

References

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