5-Amino-5-deoxy-2-C-hydroxy­methyl-2,3-O-iso­propyl­idene-d-talono-1,5-lactam

Ameijde, J.; Cowley, A.R.; Fleet, G.W.J.; Nash, R.J.; Simone, M.I.; Soengas, R.

doi:10.1107/S1600536804025292

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 60| Part 11| November 2004| Pages o2140-o2141

https://doi.org/10.1107/S1600536804025292

5-Amino-5-deoxy-2-C-hydroxymethyl-2,3-O-isopropylidene-D-talono-1,5-lactam

Jeroen van Ameijde,^a Andrew R. Cowley,^b ^* George W. J. Fleet,^a Robert J. Nash,^c Michela Iezzi Simone ^a and Raquel Soengas ^a

^aDepartment of Organic Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, England, ^bChemical Crystallography Laboratory, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, England, and ^cMolecular Nature Ltd, Insitute of Grassland and Environmental Research, Aberystwyth SY23 3EB, Wales
^*Correspondence e-mail: andrew.cowley@chem.ox.ac.uk

(Received 3 September 2004; accepted 7 October 2004; online 30 October 2004)

The title compound, C₁₀H₁₇NO₆, was prepared by carrying out three S_N2 displacements on a branched sugar derivative, one of which was not planned. Its crystal structure was determined to confirm the identity and stereochemistry of the product.

Comment

Even though the value of carbohydrate building blocks to provide access to enantiomerically pure synthetic materials is well recognized, there are no easily available branched sugar intermediates (Bols, 1996 ). The Kiliani reaction on cheap ketoses, although hitherto hardly explored, produces protected branched carbohydrates easily. Such materials are likely to have many uses, but initially we are studying the easy preparation of branched sugar mimetics in which the ring oxygen of the sugar is replaced by nitrogen (Winchester & Fleet, 1992 ; Asano et al., 2000 ). The biological properties of branched alkaloids are promising (Ichikawa & Igarashi, 1995 , Ichikawa et al., 1998 ), but the difficulties in the synthesis of such compounds have hindered a substantive investigation of these properties. The branched diacetonide (I) was readily prepared from D-fructose and was readily transformed into the trifluoromethanesulfonate (2). It was anticipated that treatment of (2) with an oxygen nucleophile would result in a single inversion of configuration at C5. However, the major product isolated, (3) had undergone inversion of configuration at both C4 and C5. The alcohol (3) was elaborated by standard reactions to the title lactam (4), the structure of which is hereby firmly established by X-ray crystallographic analysis. The configuration at C4 of the lactam (4) unequivocally demonstrates that an unexpected double inversion took place in the transformation of (2) to (3).

The NH and OH groups all form clearly defined intermolecular hydrogen bonds, linking bilayers of molecules running parallel to the crystallographic ab plane.

Figure 1
View of the title molecule, showing displacement ellipsoids at the 40% probability level. H atoms are shown as spheres of arbitrary radius.

Experimental

The lactam (4) was prepared from the diacetonide (1) derived from fructose (Hotchliss et al., 2004 ). The title material was crystallized from methanol to yield colourless plates.

Crystal data

C₁₀H₁₇NO₆
M_r = 247.25
Monoclinic, P2₁
a = 6.1266 (2) Å
b = 6.7254 (2) Å
c = 13.8419 (5) Å
β = 99.6456 (14)°
V = 562.28 (3) Å³
Z = 2
D_x = 1.460 Mg m⁻³
Mo Kα radiation
Cell parameters from 5291 reflections
θ = 5–28°
μ = 0.12 mm⁻¹
T = 150 K
Plate, colourless
0.38 × 0.38 × 0.14 mm

Data collection

Nonius KappaCCD diffractometer
ω scans
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.96, T_max = 0.98
5291 measured reflections
1372 independent reflections
1211 reflections with I > 3σ(I)
R_int = 0.030
θ_max = 27.4°
h = −7 → 7
k = −8 → 8
l = −17 → 17

Refinement

Refinement on F
R = 0.028
wR = 0.034
S = 1.10
1211 reflections
170 parameters
H atoms treated by a mixture of independent and constrained refinement
Weighting scheme: see text
(Δ/σ)_max = 0.003
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.16 e Å⁻³

Table 1
Hydrogen-bonding geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O6ⁱ	0.94 (3)	1.96 (3)	2.8510 (19)	156 (3)
O2—H2⋯O1ⁱⁱ	0.86 (3)	1.89 (3)	2.7408 (17)	169 (3)
O5—H3⋯O2ⁱⁱⁱ	0.91 (4)	1.86 (4)	2.7338 (18)	161 (3)
O6—H4⋯O5^iv	0.93 (3)	1.75 (3)	2.6610 (18)	167 (3)
Symmetry codes: (i) $[-x,y-{\script{1\over 2}},1-z]$ ; (ii) 1+x,y,z; (iii) x,1+y,z; (iv) x-1,y,z.

The weighting scheme used a Chebychev polynomial (Watkin, 1994 , Prince, 1982 ): w = {1 − [(F_o − F_c)/6σ(F)]²}²/[1.14T₀(x) + 0.561T₁(x) + 0.916T₂(x)], where x = F_c/F_max.

Friedel pairs of reflections were merged prior to use in refinement. The absolute configuration of the compound was assumed on the basis of that of the optically pure starting material. The NH and OH H atoms were located in a difference Fourier map and their coordinates and isotropic displacement parameters were subsequently refined. All other H atoms were positioned geometrically (C—H = 1.00 Å), with isotropic displacement parameters set equal to 1.2U_eq of the parent atom.

Data collection: COLLECT (Nonius, 2000 ); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: COLLECT and DENZO; program(s) used to solve structure: SIR92 (Altomare et al., 1994 ); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ); molecular graphics: ATOMS (Shape Software, 2002 ); software used to prepare material for publication: CRYSTALS.

Supporting information

Crystal structure: contains datablocks global, 4. DOI: https://doi.org/10.1107/S1600536804025292/rz6003sup1.cif

Structure factors: contains datablock 4. DOI: https://doi.org/10.1107/S1600536804025292/rz60034sup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: COLLECT and DENZO; data reduction: COLLECT and DENZO (Otwinowski & Minor, 1996); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: ATOMS (Shape Software, 2002); software used to prepare material for publication: CRYSTALS.

5-Amino-5-deoxy-2-C-hydroxymethyl-2,3-O-isopropylidene-D-talono-1,5-lactam top

Crystal data top

C₁₀H₁₇NO₆	F(000) = 264
M_r = 247.25	D_x = 1.460 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 6.1266 (2) Å	Cell parameters from 5291 reflections
b = 6.7254 (2) Å	θ = 5–28°
c = 13.8419 (5) Å	µ = 0.12 mm⁻¹
β = 99.6456 (14)°	T = 150 K
V = 562.28 (3) Å³	Plate, colourless
Z = 2	0.38 × 0.38 × 0.14 mm

Data collection top

Nonius KappaCCD diffractometer	1211 reflections with I > 3.00u(I)
Graphite monochromator	R_int = 0.030
ω scans	θ_max = 27.4°, θ_min = 5.1°
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1996)	h = −7→7
T_min = 0.96, T_max = 0.98	k = −8→8
5291 measured reflections	l = −17→17
1372 independent reflections

Refinement top

Refinement on F	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.028	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.034	Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A₀T₀(x) + A₁T₁(x) ··· + A_n-1]T_n-1(x)] where A_i are the Chebychev coefficients listed below and x = F /Fmax Method = Robust Weighting (Prince, 1982) W = [weight] [1-(deltaF/6*sigmaF)²]² A_i are: 1.14 0.561 0.916
S = 1.10	(Δ/σ)_max = 0.004
1211 reflections	Δρ_max = 0.20 e Å⁻³
170 parameters	Δρ_min = −0.16 e Å⁻³
1 restraint

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

	x	y	z	U_iso*/U_eq
N1	0.1580 (2)	0.3518 (2)	0.37174 (11)	0.0176
C1	0.1315 (2)	0.2536 (3)	0.28694 (12)	0.0160
C2	0.3054 (3)	0.2808 (2)	0.21935 (13)	0.0154
C3	0.4612 (2)	0.4553 (3)	0.24723 (10)	0.0153
C4	0.5232 (2)	0.4908 (2)	0.35601 (11)	0.0151
C5	0.3214 (2)	0.5061 (3)	0.40842 (11)	0.0161
O1	−0.0245 (2)	0.1385 (2)	0.26071 (10)	0.0239
C6	0.4241 (3)	0.0847 (3)	0.20754 (13)	0.0206
O2	0.5652 (2)	0.0291 (2)	0.29613 (10)	0.0215
O3	0.1949 (2)	0.3367 (2)	0.12375 (9)	0.0211
O4	0.3350 (2)	0.6200 (2)	0.20346 (9)	0.0182
C7	0.1964 (3)	0.5502 (3)	0.11614 (12)	0.0183
C8	0.2954 (3)	0.6069 (3)	0.02649 (14)	0.0292
C9	−0.0325 (3)	0.6348 (3)	0.11512 (15)	0.0303
O5	0.66148 (19)	0.66075 (19)	0.37549 (9)	0.0196
C10	0.2106 (3)	0.7109 (3)	0.40523 (12)	0.0203
O6	0.0666 (2)	0.7158 (2)	0.47624 (9)	0.0245
H1	0.050 (5)	0.324 (5)	0.411 (2)	0.042 (8)*
H2	0.699 (6)	0.064 (6)	0.293 (2)	0.054 (9)*
H3	0.604 (6)	0.768 (6)	0.340 (2)	0.052 (9)*
H4	−0.075 (5)	0.680 (5)	0.4463 (19)	0.038 (7)*
H31	0.6060	0.4317	0.2249	0.0186*
H41	0.6082	0.3709	0.3835	0.0179*
H51	0.3818	0.4842	0.4793	0.0194*
H61	0.5153	0.0999	0.1545	0.0252*
H62	0.3111	−0.0220	0.1891	0.0252*
H81	0.2976	0.7550	0.0203	0.0355*
H82	0.4501	0.5545	0.0336	0.0355*
H83	0.2039	0.5485	−0.0334	0.0355*
H91	−0.0270	0.7829	0.1098	0.0358*
H92	−0.0858	0.5974	0.1771	0.0358*
H93	−0.1361	0.5800	0.0578	0.0358*
H101	0.3263	0.8163	0.4205	0.0247*
H102	0.1232	0.7347	0.3385	0.0247*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0164 (7)	0.0179 (7)	0.0198 (6)	−0.0030 (5)	0.0066 (5)	0.0004 (6)
C1	0.0130 (7)	0.0138 (7)	0.0217 (8)	0.0014 (6)	0.0043 (5)	0.0041 (6)
C2	0.0166 (7)	0.0140 (7)	0.0159 (8)	−0.0015 (6)	0.0038 (6)	0.0003 (6)
C3	0.0151 (6)	0.0147 (7)	0.0167 (7)	−0.0016 (6)	0.0045 (5)	0.0009 (6)
C4	0.0140 (7)	0.0152 (8)	0.0155 (7)	−0.0008 (5)	0.0011 (5)	−0.0004 (6)
C5	0.0147 (7)	0.0186 (7)	0.0152 (7)	−0.0019 (6)	0.0026 (5)	−0.0004 (6)
O1	0.0182 (6)	0.0233 (6)	0.0307 (6)	−0.0075 (5)	0.0056 (4)	−0.0016 (6)
C6	0.0246 (8)	0.0146 (8)	0.0237 (9)	0.0000 (6)	0.0076 (6)	−0.0018 (6)
O2	0.0155 (6)	0.0166 (6)	0.0326 (7)	−0.0008 (5)	0.0047 (5)	0.0034 (5)
O3	0.0300 (7)	0.0156 (6)	0.0166 (6)	−0.0047 (5)	0.0004 (5)	−0.0006 (5)
O4	0.0234 (6)	0.0134 (5)	0.0162 (6)	−0.0013 (4)	−0.0010 (4)	0.0009 (4)
C7	0.0208 (8)	0.0164 (8)	0.0170 (8)	−0.0048 (6)	0.0011 (6)	0.0010 (6)
C8	0.0362 (10)	0.0332 (11)	0.0192 (8)	−0.0112 (9)	0.0076 (7)	0.0018 (7)
C9	0.0208 (9)	0.0315 (10)	0.0371 (10)	0.0010 (8)	0.0004 (7)	0.0023 (9)
O5	0.0141 (5)	0.0185 (6)	0.0248 (6)	−0.0042 (5)	−0.0007 (4)	−0.0012 (5)
C10	0.0178 (7)	0.0227 (8)	0.0213 (8)	−0.0004 (6)	0.0063 (6)	−0.0046 (7)
O6	0.0161 (5)	0.0370 (7)	0.0215 (6)	−0.0008 (5)	0.0060 (4)	−0.0103 (6)

Geometric parameters (Å, º) top

N1—C1	1.333 (2)	C6—H62	1.000
N1—C5	1.471 (2)	O2—H2	0.86 (3)
N1—H1	0.94 (3)	O3—C7	1.440 (2)
C1—C2	1.542 (2)	O4—C7	1.435 (2)
C1—O1	1.236 (2)	C7—C8	1.518 (2)
C2—C3	1.521 (2)	C7—C9	1.511 (2)
C2—C6	1.528 (2)	C8—H81	1.000
C2—O3	1.432 (2)	C8—H82	1.000
C3—C4	1.509 (2)	C8—H83	1.000
C3—O4	1.426 (2)	C9—H91	1.000
C3—H31	1.000	C9—H92	1.000
C4—C5	1.538 (2)	C9—H93	1.000
C4—O5	1.4215 (19)	O5—H3	0.91 (4)
C4—H41	1.000	C10—O6	1.427 (2)
C5—C10	1.533 (2)	C10—H101	1.000
C5—H51	1.000	C10—H102	1.000
C6—O2	1.427 (2)	O6—H4	0.93 (3)
C6—H61	1.000

C1—N1—C5	128.95 (13)	C2—C6—H62	108.982
C1—N1—H1	114.5 (19)	O2—C6—H62	108.982
C5—N1—H1	116 (2)	H61—C6—H62	109.467
N1—C1—C2	118.74 (14)	C6—O2—H2	109 (2)
N1—C1—O1	122.89 (15)	C2—O3—C7	108.74 (13)
C2—C1—O1	118.36 (15)	C3—O4—C7	107.81 (13)
C1—C2—C3	113.93 (13)	O3—C7—O4	105.95 (14)
C1—C2—C6	110.60 (13)	O3—C7—C8	108.57 (16)
C3—C2—C6	113.79 (13)	O4—C7—C8	110.19 (14)
C1—C2—O3	108.93 (13)	O3—C7—C9	111.03 (15)
C3—C2—O3	102.22 (13)	O4—C7—C9	107.58 (15)
C6—C2—O3	106.70 (13)	C8—C7—C9	113.27 (16)
C2—C3—C4	114.70 (13)	C7—C8—H81	109.467
C2—C3—O4	102.65 (12)	C7—C8—H82	109.467
C4—C3—O4	109.21 (13)	H81—C8—H82	109.476
C2—C3—H31	110.567	C7—C8—H83	109.467
C4—C3—H31	104.177	H81—C8—H83	109.476
O4—C3—H31	115.933	H82—C8—H83	109.476
C3—C4—C5	113.15 (13)	C7—C9—H91	109.467
C3—C4—O5	111.05 (13)	C7—C9—H92	109.467
C5—C4—O5	110.94 (13)	H91—C9—H92	109.476
C3—C4—H41	106.285	C7—C9—H93	109.467
C5—C4—H41	106.403	H91—C9—H93	109.476
O5—C4—H41	108.711	H92—C9—H93	109.476
N1—C5—C4	110.13 (13)	C4—O5—H3	112 (2)
N1—C5—C10	110.58 (13)	C5—C10—O6	108.81 (14)
C4—C5—C10	115.68 (13)	C5—C10—H101	109.637
N1—C5—H51	110.696	O6—C10—H101	109.637
C4—C5—H51	104.970	C5—C10—H102	109.637
C10—C5—H51	104.465	O6—C10—H102	109.637
C2—C6—O2	111.42 (13)	H101—C10—H102	109.467
C2—C6—H61	108.982	C10—O6—H4	109.0 (16)
O2—C6—H61	108.982

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O6ⁱ	0.94 (3)	1.96 (3)	2.8510 (19)	156 (3)
O2—H2···O1ⁱⁱ	0.86 (3)	1.89 (3)	2.7408 (17)	169 (3)
O5—H3···O2ⁱⁱⁱ	0.91 (4)	1.86 (4)	2.7338 (18)	161 (3)
O6—H4···O5^iv	0.93 (3)	1.75 (3)	2.6610 (18)	167 (3)

Symmetry codes: (i) −x, y−1/2, −z+1; (ii) x+1, y, z; (iii) x, y+1, z; (iv) x−1, y, z.

Acknowledgements

Financial support (to RS and MIS) provided through the European Community's Human Potential Programme under contract HPRN-CT-2002-00173 is gratefully acknowledged.

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