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The absolute configuration at the new stereogenic centre during the key step of the total synthesis was established byX-ray analysis of the title compound, C7H15NO4+·Cl-.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270100003231/qa0204sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S0108270100003231/qa0204Isup2.hkl
Contains datablock I

CCDC reference: 144697

Comment top

The title compound [(I); alternative name: 1,5,6-trideoxy-1,5-imino-D-gluco-heptitol hydrochloride] was prepared by palladium(II)-catalyzed aminocarbolation of (2S,3S,4R)-1-benzylamino-2,3-di-O-benzylhex-5-ene-2,3,4-triol with subsequent lactone-ring opening and deprotection (Szolcsányi et al., 1999).

The bond lengths are consistent with average values in the usual sources [International Tables for Crystallography (1992, Vol. C, Table 9.5.1.1)]. The Cl- anion is bonded in the structure by hydrogen bonds [Cl···H15 2.225 Å, Cli···H16 2.725 Å, Clii···H12 2.420 Å and Cliii···H1 2.300 Å; symmetry codes: (i) -x + 2, y - 1/2, -z; (ii) -x + 1, y - 1/2, -z; (iii) x + 1, y, z].

Experimental top

The title compound was prepared by hydrogenolysis of the benzylated diol with H2 on Pd/C at room temperature in EtOH containing a few drops of aqueous HCl. The crude product was purified by ion-exchange chromatography (H+ form, DOWEXR 50WX8–400) and recrystallized from methanol/tert-butyl methyl ether (m.p. 450–452 K, [α]D20 = +30, c = 0.55, MeOH).

Refinement top

The number of Friedel pairs in the data set is 60.

Computing details top

Data collection: Syntex P21 Software (Syntex, 1973); cell refinement: Syntex P21 Software; data reduction: XP21 (Pavelčík, 1993); program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXL93 (Sheldrick, 1993); software used to prepare material for publication: SHELXL93.

(2R,3R,4R,5S)-2-(2-Hydroxyethyl)-3,4,5-trihydroxypiperidine hydrochloride top
Crystal data top
C7H16NO4+·ClF(000) = 228
Mr = 213.66Dx = 1.478 Mg m3
Monoclinic, P21Mo Kα radiation, λ = 0.71073 Å
a = 6.891 (1) ÅCell parameters from 20 reflections
b = 7.345 (1) Åθ = 4.5–10.2°
c = 9.497 (2) ŵ = 0.38 mm1
β = 92.46 (3)°T = 293 K
V = 480.24 (14) Å3Rectangle shape, colourless
Z = 20.6 × 0.5 × 0.2 mm
Data collection top
Syntex P21
diffractometer
1222 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.048
Graphite monochromatorθmax = 30.1°, θmin = 2.2°
θ–2θ scansh = 09
Absorption correction: ψ scan
(North et al., 1968)
k = 1010
Tmin = 0.791, Tmax = 0.926l = 1313
1663 measured reflections2 standard reflections every 100 reflections
1566 independent reflections intensity decay: 15%
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)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.157H-atom parameters constrained
S = 0.91Calculated w = 1/[σ2(Fo2) + (0.1308P)2 + 0.3128P]
where P = (Fo2 + 2Fc2)/3
1461 reflections(Δ/σ)max < 0.001
118 parametersΔρmax = 0.84 e Å3
1 restraintΔρmin = 0.54 e Å3
Crystal data top
C7H16NO4+·ClV = 480.24 (14) Å3
Mr = 213.66Z = 2
Monoclinic, P21Mo Kα radiation
a = 6.891 (1) ŵ = 0.38 mm1
b = 7.345 (1) ÅT = 293 K
c = 9.497 (2) Å0.6 × 0.5 × 0.2 mm
β = 92.46 (3)°
Data collection top
Syntex P21
diffractometer
1222 reflections with I > 2σ(I)
Absorption correction: ψ scan
(North et al., 1968)
Rint = 0.048
Tmin = 0.791, Tmax = 0.9262 standard reflections every 100 reflections
1663 measured reflections intensity decay: 15%
1566 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0561 restraint
wR(F2) = 0.157H-atom parameters constrained
S = 0.91Δρmax = 0.84 e Å3
1461 reflectionsΔρmin = 0.54 e Å3
118 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Cl0.70957 (12)0.2450 (2)0.03053 (11)0.0380 (3)
O11.2925 (5)0.1946 (6)0.1045 (4)0.0495 (9)
H11.40320.20290.06990.045*
O20.8081 (4)0.2420 (6)0.5099 (3)0.0366 (6)
H80.70420.27670.54580.082*
O30.4797 (4)0.0073 (5)0.4623 (3)0.0347 (7)
H100.48590.05280.54080.055*
O40.5620 (4)0.2935 (4)0.2885 (3)0.0359 (7)
H120.46100.29550.24590.213*
N10.9569 (4)0.0187 (5)0.1771 (3)0.0257 (6)
C11.2699 (5)0.3142 (7)0.2207 (5)0.0361 (9)
H21.31640.43480.19480.050*
H31.34430.27020.29820.050*
C21.0586 (5)0.3198 (6)0.2633 (4)0.0299 (8)
H40.98740.36810.18570.050*
H51.04030.40280.34220.050*
C30.9740 (5)0.1356 (5)0.3054 (4)0.0235 (6)
H61.06150.07610.36980.050*
C40.7750 (5)0.1572 (5)0.3797 (4)0.0250 (7)
H70.69450.23670.32340.050*
C50.6711 (5)0.0216 (5)0.4039 (4)0.0274 (7)
H90.74410.09610.46890.050*
C60.6559 (5)0.1233 (5)0.2664 (4)0.0262 (7)
H110.58260.04980.20100.050*
C70.8587 (5)0.1576 (5)0.2044 (4)0.0293 (8)
H130.93230.22890.26950.050*
H140.85130.22590.11730.050*
H150.89330.09320.12140.050*
H161.06120.01780.13870.050*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl0.0247 (4)0.0467 (5)0.0429 (5)0.0003 (4)0.0047 (3)0.0084 (5)
O10.0287 (13)0.064 (2)0.055 (2)0.0137 (15)0.0130 (13)0.010 (2)
O20.0258 (11)0.046 (2)0.0378 (14)0.0004 (14)0.0027 (10)0.016 (2)
O30.0224 (12)0.046 (2)0.035 (2)0.0052 (12)0.0087 (11)0.0063 (15)
O40.0388 (14)0.034 (2)0.0353 (13)0.0165 (12)0.0053 (11)0.0045 (12)
N10.0183 (12)0.0296 (15)0.0290 (14)0.0031 (11)0.0004 (10)0.0005 (13)
C10.0232 (15)0.044 (2)0.042 (2)0.011 (2)0.0018 (15)0.003 (2)
C20.026 (2)0.026 (2)0.038 (2)0.0026 (14)0.0064 (15)0.001 (2)
C30.0161 (12)0.0276 (15)0.027 (2)0.0023 (12)0.0015 (11)0.0001 (13)
C40.0163 (12)0.029 (2)0.030 (2)0.0005 (12)0.0023 (11)0.0017 (14)
C50.0216 (14)0.031 (2)0.030 (2)0.0009 (14)0.0035 (13)0.0008 (14)
C60.0226 (15)0.026 (2)0.030 (2)0.0057 (13)0.0053 (13)0.0025 (15)
C70.026 (2)0.026 (2)0.035 (2)0.0023 (14)0.0004 (14)0.0010 (14)
Geometric parameters (Å, º) top
O1—C11.414 (6)C1—C21.495 (5)
O2—C41.412 (4)C2—C31.520 (5)
O3—C51.425 (4)C3—C41.523 (5)
O4—C61.419 (5)C4—C51.509 (5)
N1—C71.479 (5)C5—C61.512 (5)
N1—C31.500 (5)C6—C71.514 (5)
C7—N1—C3114.2 (3)C5—C4—C3113.1 (3)
O1—C1—C2107.6 (3)O3—C5—C6108.2 (3)
C1—C2—C3113.8 (3)O3—C5—C4110.8 (3)
N1—C3—C2109.8 (3)C6—C5—C4110.4 (3)
N1—C3—C4109.6 (3)O4—C6—C5110.9 (3)
C2—C3—C4110.9 (3)O4—C6—C7108.6 (3)
O2—C4—C5110.1 (3)C5—C6—C7108.8 (3)
O2—C4—C3106.0 (3)N1—C7—C6109.3 (3)

Experimental details

Crystal data
Chemical formulaC7H16NO4+·Cl
Mr213.66
Crystal system, space groupMonoclinic, P21
Temperature (K)293
a, b, c (Å)6.891 (1), 7.345 (1), 9.497 (2)
β (°) 92.46 (3)
V3)480.24 (14)
Z2
Radiation typeMo Kα
µ (mm1)0.38
Crystal size (mm)0.6 × 0.5 × 0.2
Data collection
DiffractometerSyntex P21
diffractometer
Absorption correctionψ scan
(North et al., 1968)
Tmin, Tmax0.791, 0.926
No. of measured, independent and
observed [I > 2σ(I)] reflections
1663, 1566, 1222
Rint0.048
(sin θ/λ)max1)0.705
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.056, 0.157, 0.91
No. of reflections1461
No. of parameters118
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.84, 0.54

Computer programs: Syntex P21 Software (Syntex, 1973), Syntex P21 Software, XP21 (Pavelčík, 1993), SHELXS86 (Sheldrick, 1990), SHELXL93 (Sheldrick, 1993), SHELXL93.

Selected geometric parameters (Å, º) top
O1—C11.414 (6)C1—C21.495 (5)
O2—C41.412 (4)C2—C31.520 (5)
O3—C51.425 (4)C3—C41.523 (5)
O4—C61.419 (5)C4—C51.509 (5)
N1—C71.479 (5)C5—C61.512 (5)
N1—C31.500 (5)C6—C71.514 (5)
C7—N1—C3114.2 (3)C5—C4—C3113.1 (3)
O1—C1—C2107.6 (3)O3—C5—C6108.2 (3)
C1—C2—C3113.8 (3)O3—C5—C4110.8 (3)
N1—C3—C2109.8 (3)C6—C5—C4110.4 (3)
N1—C3—C4109.6 (3)O4—C6—C5110.9 (3)
C2—C3—C4110.9 (3)O4—C6—C7108.6 (3)
O2—C4—C5110.1 (3)C5—C6—C7108.8 (3)
O2—C4—C3106.0 (3)N1—C7—C6109.3 (3)
 

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