organic compounds
(S)-3-Dimethylamino-2-{(4S,5R)-5-[(R)-2,2-dimethyl-1,3-dioxolan-4-yl]-2,2-dimethyl-1,3-dioxolan-4-yl}-2-hydroxypropanoic acid
aDepartment of Organic Chemistry, Chemical Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, England, and bDepartment of Chemical Crystallography, Chemical Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, England
*Correspondence e-mail: sarah.jenkinson@chem.ox.ac.uk
The Kiliani reaction on 1-deoxy-(N,N-dimethylamino)-D-fructose, itself readily available from reaction of dimethylamine and D-glucose, proceeded to give access to the title β-sugar amino acid, C15H27NO7. X-ray crystallography determined the stereochemistry at the newly formed chiral center. There are two molecules in the they are related by a pseudo-twofold rotation axis and have very similar geometries, differing only in the conformation of one of the acetonide rings. All the acetonide rings adopt envelope conformations; the flap atom is oxygen in three of the rings, but carbon in one of them. There are two strong hydrogen bonds between the two independent molecules, and further weak hydrogen bonds link the molecules to form infinite chains running parallel to the a axis.
Related literature
For related literature see: Risseeuw et al. (2007); Hotchkiss et al. (2004, 2008); Soengas et al. (2005); Parker et al. (2006); Simone et al. (2007). For the weighting scheme, see: Prince (1982); Watkin (1994).
Experimental
Crystal data
|
Refinement
|
Data collection: COLLECT (Nonius, 2001); cell DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK; program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS.
Supporting information
https://doi.org/10.1107/S1600536807066676/cf2175sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807066676/cf2175Isup2.hkl
The title compound was prepared as described by Hotchkiss et al. (2008) and shown in the reaction scheme of Fig. 1, and was recrystallized from ethyl acetate. m.p.: 453 K decomposed; [α]D23 +19.3 (c, 1.0 in water).
In the absence of significant σ(F2).
Friedel pairs were merged and the was assigned from the starting material. The on F values, used only data for which F2 > 3The H atoms were all located in a difference map, but those attached to carbon atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H in the range 0.93–0.98, N—H in the range 0.86–0.89 N—H to 0.86 O—H = 0.82 Å) and Uiso(H) (in the range 1.2–1.5 times Ueq of the parent atom), after which the positions were refined with riding constraints.
Sugar amino acids are a versatile class of conformationally biased building blocks, and have use as both glyco- and peptido-mimetics (Risseeuw et al., 2007). The Kiliani reaction on β-sugar amino acids. The reaction of 1-deoxy-1-(N,N-dimethylamino)-D-fructose, 2, an Amadori product readily available from D-glucose, 1, with sodium cyanide in water was found to give, after acetonide protection, the title compound, 3, as the major product. The stereochemistry at C-2 was unequivocally assigned by X-ray crystallography (Fig. 2) and the absolute stereochemistry was determined by the use of D-glucose as the starting material.
has been successfully utilized in the synthesis of branched carbohydrate building blocks (Hotchkiss et al., 2004; Soengas et al., 2005; Parker et al., 2006; Simone et al., 2007) to produce, for example, methyl or hydroxymethyl branched With Amadori products, 1-amino-1-deoxy-ketoses, as substrates, the Kiliani ascension should provide access toThe
contains of two crystallographically distinct molecules which are related by a pseudo-2-fold rotation axis. These are similar in geometry with the exception of one of the isopropylidene rings: in the first molecule the atoms C20, O13, O14 and C28 are approximately coplanar while C21 is displaced from this plane, whereas in the second molecule C120, C121, O113 and C128 are approximately coplanar while O114 is displaced. The r.m.s. bond length deviation for the two molecules, excluding hydrogen atoms, is 0.007 Å.Hydrogen bonding links molecules to form infinite chains running parallel to the crystallographic a axis (Fig. 3). There are two weak hydrogen bonds between the layers and two strong hydrogen bonds linking the two molecules in the
(Fig. 4).For related literature see: Risseeuw et al. (2007); Hotchkiss et al. (2004, 2008); Soengas et al. (2005); Parker et al. (2006); Simone et al. (2007). For the
weighting scheme, see: Prince (1982); Watkin (1994).Data collection: COLLECT (Nonius, 2001); cell
DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).C15H27NO7 | F(000) = 720 |
Mr = 333.38 | Dx = 1.299 Mg m−3 |
Monoclinic, P21 | Mo Kα radiation, λ = 0.71073 Å |
a = 5.7881 (2) Å | Cell parameters from 13496 reflections |
b = 16.7077 (4) Å | θ = 5–28° |
c = 17.8572 (5) Å | µ = 0.10 mm−1 |
β = 99.1141 (8)° | T = 150 K |
V = 1705.09 (9) Å3 | Fragment, colourless |
Z = 4 | 0.40 × 0.10 × 0.08 mm |
Nonius KappaCCD diffractometer | 3474 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
ω scans | θmax = 27.5°, θmin = 5.1° |
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) | h = −7→7 |
Tmin = 0.96, Tmax = 1.01 | k = −20→21 |
13496 measured reflections | l = −23→23 |
4000 independent reflections |
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)] = 0.032 | H-atom parameters constrained |
wR(F2) = 0.033 | w = [1-(Fo-Fc)2/36σ2(F)]2/[0.462T0(x) + 0.141T1(x) + 0.209T2(x)] where Ti are Chebychev polynomials and x = Fc/Fmax (Prince, 1982; Watkin, 1994) |
S = 1.09 | (Δ/σ)max = 0.003 |
3239 reflections | Δρmax = 0.18 e Å−3 |
415 parameters | Δρmin = −0.15 e Å−3 |
1 restraint |
C15H27NO7 | V = 1705.09 (9) Å3 |
Mr = 333.38 | Z = 4 |
Monoclinic, P21 | Mo Kα radiation |
a = 5.7881 (2) Å | µ = 0.10 mm−1 |
b = 16.7077 (4) Å | T = 150 K |
c = 17.8572 (5) Å | 0.40 × 0.10 × 0.08 mm |
β = 99.1141 (8)° |
Nonius KappaCCD diffractometer | 4000 independent reflections |
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) | 3474 reflections with I > 2σ(I) |
Tmin = 0.96, Tmax = 1.01 | Rint = 0.034 |
13496 measured reflections |
R[F2 > 2σ(F2)] = 0.032 | 1 restraint |
wR(F2) = 0.033 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.18 e Å−3 |
3239 reflections | Δρmin = −0.15 e Å−3 |
415 parameters |
x | y | z | Uiso*/Ueq | ||
C116 | 0.4385 (4) | 0.61358 (13) | 0.18160 (11) | 0.0229 | |
C117 | 0.5150 (3) | 0.70044 (12) | 0.20298 (11) | 0.0214 | |
C118 | 0.3803 (4) | 0.75579 (12) | 0.14222 (11) | 0.0215 | |
C119 | 0.4380 (4) | 0.74189 (12) | 0.06211 (12) | 0.0245 | |
C120 | 0.2595 (4) | 0.69110 (13) | 0.01196 (12) | 0.0281 | |
C121 | 0.0366 (4) | 0.73492 (15) | −0.02378 (12) | 0.0309 | |
O108 | 0.5915 (3) | 0.56731 (10) | 0.16763 (11) | 0.0411 | |
O109 | 0.2243 (3) | 0.59883 (9) | 0.17987 (9) | 0.0291 | |
O110 | 0.7593 (2) | 0.70916 (9) | 0.20458 (9) | 0.0257 | |
O111 | 0.4370 (3) | 0.83813 (9) | 0.15861 (8) | 0.0247 | |
O112 | 0.4449 (3) | 0.82134 (10) | 0.03206 (8) | 0.0302 | |
O113 | 0.3587 (3) | 0.66311 (11) | −0.05185 (9) | 0.0356 | |
O114 | 0.0662 (3) | 0.74545 (10) | −0.10091 (9) | 0.0292 | |
C122 | 0.4465 (4) | 0.72297 (12) | 0.27944 (11) | 0.0222 | |
N102 | 0.5117 (3) | 0.66327 (11) | 0.34183 (9) | 0.0225 | |
C123 | 0.4395 (4) | 0.69477 (15) | 0.41273 (12) | 0.0308 | |
C124 | 0.7666 (4) | 0.64198 (15) | 0.35724 (14) | 0.0332 | |
C125 | 0.5228 (4) | 0.87319 (13) | 0.09473 (12) | 0.0254 | |
C126 | 0.7880 (4) | 0.87748 (14) | 0.11015 (14) | 0.0305 | |
C127 | 0.4103 (4) | 0.95410 (13) | 0.07883 (14) | 0.0308 | |
C128 | 0.1957 (4) | 0.67786 (13) | −0.11891 (12) | 0.0250 | |
C130 | 0.3287 (5) | 0.69882 (16) | −0.18191 (15) | 0.0372 | |
C129 | 0.0342 (5) | 0.60661 (16) | −0.13784 (16) | 0.0413 | |
C16 | 0.3613 (4) | 0.46972 (13) | 0.33186 (11) | 0.0221 | |
C17 | 0.2219 (3) | 0.39235 (12) | 0.30686 (11) | 0.0207 | |
C18 | 0.0715 (3) | 0.37226 (12) | 0.36854 (11) | 0.0214 | |
C19 | 0.2109 (4) | 0.35053 (13) | 0.44690 (12) | 0.0232 | |
C20 | 0.2117 (4) | 0.41812 (14) | 0.50374 (13) | 0.0321 | |
C21 | −0.0232 (5) | 0.45509 (17) | 0.51083 (14) | 0.0445 | |
O8 | 0.5763 (3) | 0.46309 (11) | 0.34502 (12) | 0.0422 | |
O9 | 0.2444 (3) | 0.53219 (9) | 0.33683 (9) | 0.0284 | |
O10 | 0.3781 (2) | 0.32903 (9) | 0.29844 (9) | 0.0251 | |
O11 | −0.0735 (2) | 0.30306 (9) | 0.34789 (8) | 0.0232 | |
O12 | 0.0913 (3) | 0.28280 (9) | 0.47036 (9) | 0.0286 | |
O13 | 0.2906 (3) | 0.38992 (10) | 0.57957 (8) | 0.0345 | |
O14 | 0.0240 (4) | 0.48999 (11) | 0.58459 (10) | 0.0500 | |
C22 | 0.0472 (3) | 0.40421 (12) | 0.23363 (11) | 0.0210 | |
N2 | 0.1429 (3) | 0.44201 (10) | 0.16870 (9) | 0.0204 | |
C23 | −0.0510 (4) | 0.45073 (13) | 0.10267 (12) | 0.0247 | |
C24 | 0.3421 (4) | 0.39788 (14) | 0.14406 (13) | 0.0268 | |
C25 | −0.0112 (4) | 0.24115 (13) | 0.40337 (12) | 0.0239 | |
C26 | 0.1574 (4) | 0.18220 (13) | 0.37676 (13) | 0.0283 | |
C27 | −0.2313 (4) | 0.20088 (15) | 0.41883 (14) | 0.0309 | |
C28 | 0.1693 (5) | 0.43430 (14) | 0.63045 (13) | 0.0353 | |
C29 | 0.0209 (5) | 0.37758 (18) | 0.66863 (17) | 0.0465 | |
C30 | 0.3447 (6) | 0.48027 (18) | 0.68589 (16) | 0.0518 | |
H1181 | 0.2144 | 0.7487 | 0.1423 | 0.0252* | |
H1191 | 0.5917 | 0.7168 | 0.0646 | 0.0293* | |
H1201 | 0.2207 | 0.6450 | 0.0408 | 0.0337* | |
H1211 | 0.0253 | 0.7867 | −0.0002 | 0.0376* | |
H1212 | −0.1033 | 0.7032 | −0.0199 | 0.0368* | |
H1221 | 0.5202 | 0.7735 | 0.2962 | 0.0258* | |
H1222 | 0.2768 | 0.7284 | 0.2732 | 0.0254* | |
H1231 | 0.4711 | 0.6537 | 0.4509 | 0.0459* | |
H1233 | 0.5303 | 0.7422 | 0.4267 | 0.0453* | |
H1232 | 0.2760 | 0.7072 | 0.4021 | 0.0450* | |
H1241 | 0.7978 | 0.6080 | 0.4012 | 0.0490* | |
H1243 | 0.8570 | 0.6911 | 0.3649 | 0.0489* | |
H1242 | 0.8073 | 0.6134 | 0.3141 | 0.0483* | |
H1261 | 0.8415 | 0.9000 | 0.0662 | 0.0460* | |
H1262 | 0.8342 | 0.9121 | 0.1535 | 0.0454* | |
H1263 | 0.8507 | 0.8252 | 0.1202 | 0.0451* | |
H1271 | 0.4619 | 0.9783 | 0.0352 | 0.0453* | |
H1272 | 0.4513 | 0.9888 | 0.1220 | 0.0449* | |
H1273 | 0.2425 | 0.9481 | 0.0687 | 0.0443* | |
H1301 | 0.2217 | 0.7150 | −0.2268 | 0.0566* | |
H1302 | 0.4370 | 0.7422 | −0.1661 | 0.0565* | |
H1303 | 0.4179 | 0.6536 | −0.1945 | 0.0565* | |
H1291 | −0.0809 | 0.6189 | −0.1822 | 0.0617* | |
H1292 | −0.0451 | 0.5955 | −0.0955 | 0.0615* | |
H1293 | 0.1258 | 0.5604 | −0.1487 | 0.0622* | |
H181 | −0.0296 | 0.4172 | 0.3728 | 0.0237* | |
H191 | 0.3710 | 0.3357 | 0.4429 | 0.0264* | |
H201 | 0.3210 | 0.4583 | 0.4911 | 0.0357* | |
H211 | −0.0701 | 0.4960 | 0.4730 | 0.0524* | |
H212 | −0.1466 | 0.4145 | 0.5069 | 0.0521* | |
H222 | −0.0791 | 0.4377 | 0.2456 | 0.0239* | |
H221 | −0.0117 | 0.3514 | 0.2167 | 0.0247* | |
H231 | 0.0118 | 0.4763 | 0.0624 | 0.0361* | |
H232 | −0.1710 | 0.4831 | 0.1193 | 0.0354* | |
H233 | −0.1099 | 0.3991 | 0.0872 | 0.0355* | |
H241 | 0.3790 | 0.4232 | 0.0985 | 0.0408* | |
H242 | 0.4751 | 0.3989 | 0.1848 | 0.0403* | |
H243 | 0.2889 | 0.3436 | 0.1335 | 0.0399* | |
H262 | 0.2116 | 0.1456 | 0.4172 | 0.0424* | |
H261 | 0.2886 | 0.2090 | 0.3608 | 0.0418* | |
H263 | 0.0743 | 0.1521 | 0.3350 | 0.0414* | |
H272 | −0.1849 | 0.1570 | 0.4539 | 0.0465* | |
H271 | −0.3277 | 0.2390 | 0.4395 | 0.0470* | |
H273 | −0.3152 | 0.1817 | 0.3708 | 0.0462* | |
H292 | −0.0685 | 0.4070 | 0.7011 | 0.0699* | |
H291 | 0.1215 | 0.3398 | 0.6993 | 0.0692* | |
H293 | −0.0862 | 0.3518 | 0.6295 | 0.0696* | |
H302 | 0.2616 | 0.5129 | 0.7176 | 0.0760* | |
H301 | 0.4457 | 0.4426 | 0.7178 | 0.0759* | |
H303 | 0.4375 | 0.5141 | 0.6576 | 0.0749* | |
H21 | 0.1925 | 0.4920 | 0.1815 | 0.0296* | |
H1021 | 0.4300 | 0.6182 | 0.3304 | 0.0330* | |
H1101 | 0.8115 | 0.6662 | 0.1944 | 0.0382* | |
H101 | 0.5088 | 0.3466 | 0.3164 | 0.0387* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C116 | 0.0305 (11) | 0.0199 (9) | 0.0184 (9) | −0.0035 (8) | 0.0043 (8) | 0.0006 (8) |
C117 | 0.0232 (9) | 0.0189 (9) | 0.0218 (9) | −0.0018 (8) | 0.0026 (7) | 0.0014 (8) |
C118 | 0.0266 (10) | 0.0171 (9) | 0.0207 (9) | −0.0018 (8) | 0.0038 (7) | 0.0003 (7) |
C119 | 0.0334 (11) | 0.0191 (10) | 0.0216 (10) | −0.0009 (9) | 0.0057 (8) | 0.0004 (8) |
C120 | 0.0402 (12) | 0.0235 (11) | 0.0205 (10) | 0.0002 (9) | 0.0045 (8) | −0.0002 (8) |
C121 | 0.0356 (12) | 0.0336 (12) | 0.0238 (11) | 0.0030 (10) | 0.0057 (9) | −0.0032 (9) |
O108 | 0.0392 (9) | 0.0231 (8) | 0.0630 (12) | 0.0017 (7) | 0.0145 (8) | −0.0123 (8) |
O109 | 0.0315 (8) | 0.0211 (7) | 0.0347 (8) | −0.0040 (6) | 0.0052 (6) | −0.0009 (6) |
O110 | 0.0237 (7) | 0.0214 (7) | 0.0329 (8) | 0.0007 (6) | 0.0066 (6) | 0.0003 (6) |
O111 | 0.0337 (8) | 0.0163 (7) | 0.0252 (7) | −0.0011 (6) | 0.0083 (6) | −0.0015 (6) |
O112 | 0.0463 (9) | 0.0225 (8) | 0.0215 (7) | −0.0075 (7) | 0.0049 (6) | 0.0010 (6) |
O113 | 0.0433 (9) | 0.0360 (9) | 0.0246 (8) | 0.0158 (8) | −0.0041 (7) | −0.0071 (7) |
O114 | 0.0378 (8) | 0.0225 (7) | 0.0265 (8) | 0.0059 (7) | 0.0023 (6) | −0.0008 (6) |
C122 | 0.0258 (10) | 0.0191 (9) | 0.0211 (10) | 0.0003 (8) | 0.0019 (8) | 0.0001 (8) |
N102 | 0.0253 (8) | 0.0209 (8) | 0.0205 (8) | −0.0055 (7) | 0.0009 (6) | 0.0000 (7) |
C123 | 0.0378 (12) | 0.0339 (12) | 0.0208 (10) | −0.0050 (10) | 0.0047 (9) | −0.0014 (9) |
C124 | 0.0248 (11) | 0.0348 (12) | 0.0375 (12) | 0.0002 (9) | −0.0026 (9) | 0.0089 (10) |
C125 | 0.0307 (11) | 0.0238 (10) | 0.0220 (10) | −0.0030 (9) | 0.0049 (8) | 0.0007 (8) |
C126 | 0.0321 (11) | 0.0257 (11) | 0.0347 (12) | −0.0004 (9) | 0.0084 (9) | 0.0003 (9) |
C127 | 0.0312 (11) | 0.0213 (10) | 0.0384 (12) | −0.0015 (9) | 0.0012 (9) | 0.0061 (9) |
C128 | 0.0330 (11) | 0.0203 (9) | 0.0210 (9) | 0.0019 (9) | 0.0023 (8) | 0.0004 (8) |
C130 | 0.0447 (14) | 0.0343 (13) | 0.0346 (12) | −0.0017 (11) | 0.0119 (10) | −0.0031 (10) |
C129 | 0.0507 (15) | 0.0291 (12) | 0.0448 (14) | −0.0097 (11) | 0.0097 (12) | −0.0110 (11) |
C16 | 0.0237 (9) | 0.0210 (10) | 0.0210 (9) | −0.0016 (8) | 0.0015 (7) | 0.0022 (7) |
C17 | 0.0197 (9) | 0.0168 (9) | 0.0253 (10) | 0.0013 (7) | 0.0029 (7) | 0.0006 (7) |
C18 | 0.0212 (9) | 0.0196 (9) | 0.0227 (9) | −0.0017 (8) | 0.0009 (7) | 0.0007 (8) |
C19 | 0.0250 (10) | 0.0200 (9) | 0.0233 (10) | 0.0024 (8) | −0.0004 (7) | 0.0017 (8) |
C20 | 0.0452 (13) | 0.0225 (11) | 0.0253 (11) | 0.0027 (9) | −0.0044 (9) | 0.0000 (9) |
C21 | 0.0644 (17) | 0.0374 (14) | 0.0273 (12) | 0.0278 (13) | −0.0060 (11) | −0.0032 (10) |
O8 | 0.0214 (7) | 0.0275 (9) | 0.0734 (13) | −0.0021 (7) | −0.0059 (8) | −0.0020 (8) |
O9 | 0.0265 (8) | 0.0200 (7) | 0.0380 (9) | −0.0021 (6) | 0.0034 (6) | −0.0022 (6) |
O10 | 0.0206 (7) | 0.0203 (7) | 0.0342 (8) | 0.0025 (6) | 0.0041 (6) | −0.0014 (6) |
O11 | 0.0242 (7) | 0.0210 (7) | 0.0234 (7) | −0.0037 (6) | 0.0011 (5) | 0.0042 (6) |
O12 | 0.0394 (9) | 0.0208 (7) | 0.0239 (7) | −0.0009 (6) | −0.0004 (6) | 0.0027 (6) |
O13 | 0.0485 (10) | 0.0305 (9) | 0.0212 (8) | 0.0106 (8) | −0.0046 (7) | −0.0022 (6) |
O14 | 0.0876 (15) | 0.0320 (9) | 0.0267 (9) | 0.0296 (10) | −0.0026 (9) | −0.0032 (8) |
C22 | 0.0207 (9) | 0.0189 (9) | 0.0237 (10) | −0.0026 (8) | 0.0044 (7) | 0.0000 (8) |
N2 | 0.0216 (8) | 0.0173 (8) | 0.0222 (8) | −0.0018 (6) | 0.0027 (6) | −0.0013 (7) |
C23 | 0.0254 (10) | 0.0253 (10) | 0.0222 (10) | 0.0005 (8) | 0.0005 (7) | −0.0006 (8) |
C24 | 0.0252 (10) | 0.0264 (10) | 0.0298 (11) | 0.0013 (9) | 0.0072 (8) | −0.0029 (9) |
C25 | 0.0280 (10) | 0.0213 (10) | 0.0218 (10) | −0.0016 (8) | 0.0020 (8) | 0.0028 (8) |
C26 | 0.0275 (10) | 0.0226 (10) | 0.0348 (12) | 0.0018 (8) | 0.0050 (9) | 0.0009 (9) |
C27 | 0.0295 (11) | 0.0295 (11) | 0.0350 (12) | −0.0010 (9) | 0.0089 (9) | 0.0061 (9) |
C28 | 0.0532 (14) | 0.0247 (11) | 0.0253 (11) | 0.0118 (10) | −0.0018 (10) | −0.0021 (9) |
C29 | 0.0488 (15) | 0.0429 (15) | 0.0475 (15) | 0.0105 (13) | 0.0072 (12) | 0.0063 (13) |
C30 | 0.079 (2) | 0.0387 (15) | 0.0340 (14) | −0.0050 (15) | −0.0020 (13) | −0.0106 (12) |
C116—C117 | 1.547 (3) | C16—C17 | 1.552 (3) |
C116—O108 | 1.231 (3) | C16—O8 | 1.234 (3) |
C116—O109 | 1.260 (3) | C16—O9 | 1.255 (3) |
C117—C118 | 1.540 (3) | C17—C18 | 1.545 (3) |
C117—O110 | 1.417 (2) | C17—O10 | 1.415 (2) |
C117—C122 | 1.528 (3) | C17—C22 | 1.534 (3) |
C118—C119 | 1.537 (3) | C18—C19 | 1.544 (3) |
C118—O111 | 1.434 (2) | C18—O11 | 1.442 (2) |
C118—H1181 | 0.968 | C18—H181 | 0.962 |
C119—C120 | 1.515 (3) | C19—C20 | 1.518 (3) |
C119—O112 | 1.435 (3) | C19—O12 | 1.424 (3) |
C119—H1191 | 0.978 | C19—H191 | 0.973 |
C120—C121 | 1.532 (3) | C20—C21 | 1.517 (4) |
C120—O113 | 1.433 (3) | C20—O13 | 1.438 (3) |
C120—H1201 | 0.973 | C20—H201 | 0.973 |
C121—O114 | 1.425 (3) | C21—O14 | 1.427 (3) |
C121—H1211 | 0.969 | C21—H211 | 0.969 |
C121—H1212 | 0.979 | C21—H212 | 0.980 |
O110—H1101 | 0.810 | O10—H101 | 0.828 |
O111—C125 | 1.439 (2) | O11—C25 | 1.438 (2) |
O112—C125 | 1.431 (3) | O12—C25 | 1.429 (3) |
O113—C128 | 1.423 (3) | O13—C28 | 1.439 (3) |
O114—C128 | 1.420 (3) | O14—C28 | 1.423 (3) |
C122—N102 | 1.499 (3) | C22—N2 | 1.501 (3) |
C122—H1221 | 0.971 | C22—H222 | 0.970 |
C122—H1222 | 0.975 | C22—H221 | 0.976 |
N102—C123 | 1.491 (3) | N2—C23 | 1.500 (3) |
N102—C124 | 1.500 (3) | N2—C24 | 1.492 (3) |
N102—H1021 | 0.896 | N2—H21 | 0.900 |
C123—H1231 | 0.964 | C23—H231 | 0.956 |
C123—H1233 | 0.962 | C23—H232 | 0.964 |
C123—H1232 | 0.958 | C23—H233 | 0.953 |
C124—H1241 | 0.962 | C24—H241 | 0.971 |
C124—H1243 | 0.971 | C24—H242 | 0.973 |
C124—H1242 | 0.967 | C24—H243 | 0.967 |
C125—C126 | 1.518 (3) | C25—C26 | 1.515 (3) |
C125—C127 | 1.508 (3) | C25—C27 | 1.504 (3) |
C126—H1261 | 0.964 | C26—H262 | 0.960 |
C126—H1262 | 0.969 | C26—H261 | 0.963 |
C126—H1263 | 0.952 | C26—H263 | 0.962 |
C127—H1271 | 0.966 | C27—H272 | 0.974 |
C127—H1272 | 0.964 | C27—H271 | 0.958 |
C127—H1273 | 0.965 | C27—H273 | 0.971 |
C128—C130 | 1.502 (3) | C28—C29 | 1.512 (4) |
C128—C129 | 1.518 (3) | C28—C30 | 1.511 (4) |
C130—H1301 | 0.971 | C29—H292 | 0.970 |
C130—H1302 | 0.970 | C29—H291 | 0.968 |
C130—H1303 | 0.962 | C29—H293 | 0.960 |
C129—H1291 | 0.973 | C30—H302 | 0.967 |
C129—H1292 | 0.962 | C30—H301 | 0.978 |
C129—H1293 | 0.973 | C30—H303 | 0.974 |
C117—C116—O108 | 116.90 (18) | C17—C16—O8 | 116.28 (18) |
C117—C116—O109 | 115.55 (18) | C17—C16—O9 | 116.84 (17) |
O108—C116—O109 | 127.5 (2) | O8—C16—O9 | 126.9 (2) |
C116—C117—C118 | 107.24 (15) | C16—C17—C18 | 107.57 (16) |
C116—C117—O110 | 110.29 (16) | C16—C17—O10 | 109.98 (15) |
C118—C117—O110 | 110.14 (16) | C18—C17—O10 | 110.78 (16) |
C116—C117—C122 | 110.32 (16) | C16—C17—C22 | 112.36 (16) |
C118—C117—C122 | 107.92 (16) | C18—C17—C22 | 105.42 (15) |
O110—C117—C122 | 110.84 (16) | O10—C17—C22 | 110.61 (16) |
C117—C118—C119 | 113.87 (17) | C17—C18—C19 | 115.13 (16) |
C117—C118—O111 | 111.02 (15) | C17—C18—O11 | 111.26 (16) |
C119—C118—O111 | 104.98 (16) | C19—C18—O11 | 104.04 (15) |
C117—C118—H1181 | 108.5 | C17—C18—H181 | 107.8 |
C119—C118—H1181 | 110.2 | C19—C18—H181 | 110.4 |
O111—C118—H1181 | 108.1 | O11—C18—H181 | 108.0 |
C118—C119—C120 | 113.97 (17) | C18—C19—C20 | 112.14 (17) |
C118—C119—O112 | 103.37 (16) | C18—C19—O12 | 104.19 (15) |
C120—C119—O112 | 110.72 (17) | C20—C19—O12 | 110.16 (18) |
C118—C119—H1191 | 110.7 | C18—C19—H191 | 111.1 |
C120—C119—H1191 | 108.5 | C20—C19—H191 | 109.7 |
O112—C119—H1191 | 109.5 | O12—C19—H191 | 109.4 |
C119—C120—C121 | 115.40 (19) | C19—C20—C21 | 116.8 (2) |
C119—C120—O113 | 109.34 (18) | C19—C20—O13 | 110.66 (17) |
C121—C120—O113 | 103.99 (16) | C21—C20—O13 | 102.13 (19) |
C119—C120—H1201 | 108.8 | C19—C20—H201 | 107.0 |
C121—C120—H1201 | 110.5 | C21—C20—H201 | 111.3 |
O113—C120—H1201 | 108.6 | O13—C20—H201 | 108.8 |
C120—C121—O114 | 103.85 (17) | C20—C21—O14 | 101.6 (2) |
C120—C121—H1211 | 110.8 | C20—C21—H211 | 112.6 |
O114—C121—H1211 | 109.7 | O14—C21—H211 | 110.3 |
C120—C121—H1212 | 111.3 | C20—C21—H212 | 111.4 |
O114—C121—H1212 | 111.2 | O14—C21—H212 | 112.3 |
H1211—C121—H1212 | 109.8 | H211—C21—H212 | 108.6 |
C117—O110—H1101 | 108.1 | C17—O10—H101 | 104.7 |
C118—O111—C125 | 108.99 (15) | C18—O11—C25 | 109.17 (14) |
C119—O112—C125 | 106.95 (15) | C19—O12—C25 | 107.31 (15) |
C120—O113—C128 | 108.48 (16) | C20—O13—C28 | 108.15 (16) |
C121—O114—C128 | 105.60 (16) | C21—O14—C28 | 105.86 (17) |
C117—C122—N102 | 115.47 (16) | C17—C22—N2 | 116.01 (15) |
C117—C122—H1221 | 109.1 | C17—C22—H222 | 107.8 |
N102—C122—H1221 | 107.6 | N2—C22—H222 | 108.0 |
C117—C122—H1222 | 108.6 | C17—C22—H221 | 107.4 |
N102—C122—H1222 | 106.1 | N2—C22—H221 | 107.1 |
H1221—C122—H1222 | 109.9 | H222—C22—H221 | 110.6 |
C122—N102—C123 | 108.96 (16) | C22—N2—C23 | 109.03 (15) |
C122—N102—C124 | 114.76 (17) | C22—N2—C24 | 114.62 (16) |
C123—N102—C124 | 109.14 (17) | C23—N2—C24 | 109.44 (16) |
C122—N102—H1021 | 109.2 | C22—N2—H21 | 109.7 |
C123—N102—H1021 | 106.4 | C23—N2—H21 | 106.1 |
C124—N102—H1021 | 108.1 | C24—N2—H21 | 107.6 |
N102—C123—H1231 | 107.6 | N2—C23—H231 | 107.9 |
N102—C123—H1233 | 107.2 | N2—C23—H232 | 107.3 |
H1231—C123—H1233 | 111.6 | H231—C23—H232 | 111.1 |
N102—C123—H1232 | 108.1 | N2—C23—H233 | 109.2 |
H1231—C123—H1232 | 111.4 | H231—C23—H233 | 110.3 |
H1233—C123—H1232 | 110.8 | H232—C23—H233 | 110.8 |
N102—C124—H1241 | 110.0 | N2—C24—H241 | 108.3 |
N102—C124—H1243 | 108.5 | N2—C24—H242 | 109.1 |
H1241—C124—H1243 | 110.9 | H241—C24—H242 | 111.5 |
N102—C124—H1242 | 109.1 | N2—C24—H243 | 106.5 |
H1241—C124—H1242 | 108.7 | H241—C24—H243 | 110.6 |
H1243—C124—H1242 | 109.5 | H242—C24—H243 | 110.7 |
O111—C125—O112 | 105.55 (16) | O11—C25—O12 | 104.59 (16) |
O111—C125—C126 | 109.99 (17) | O11—C25—C26 | 110.80 (17) |
O112—C125—C126 | 110.79 (18) | O12—C25—C26 | 112.11 (17) |
O111—C125—C127 | 108.73 (17) | O11—C25—C27 | 108.73 (17) |
O112—C125—C127 | 108.80 (17) | O12—C25—C27 | 108.40 (18) |
C126—C125—C127 | 112.70 (18) | C26—C25—C27 | 111.91 (18) |
C125—C126—H1261 | 108.5 | C25—C26—H262 | 109.2 |
C125—C126—H1262 | 108.4 | C25—C26—H261 | 111.6 |
H1261—C126—H1262 | 109.5 | H262—C26—H261 | 109.9 |
C125—C126—H1263 | 109.6 | C25—C26—H263 | 108.4 |
H1261—C126—H1263 | 110.4 | H262—C26—H263 | 108.2 |
H1262—C126—H1263 | 110.4 | H261—C26—H263 | 109.5 |
C125—C127—H1271 | 110.4 | C25—C27—H272 | 107.4 |
C125—C127—H1272 | 110.1 | C25—C27—H271 | 109.5 |
H1271—C127—H1272 | 109.0 | H272—C27—H271 | 111.9 |
C125—C127—H1273 | 109.5 | C25—C27—H273 | 107.7 |
H1271—C127—H1273 | 108.9 | H272—C27—H273 | 111.6 |
H1272—C127—H1273 | 109.0 | H271—C27—H273 | 108.6 |
O113—C128—O114 | 104.50 (16) | O13—C28—O14 | 106.07 (18) |
O113—C128—C130 | 108.70 (19) | O13—C28—C29 | 109.3 (2) |
O114—C128—C130 | 109.61 (18) | O14—C28—C29 | 110.1 (2) |
O113—C128—C129 | 110.74 (19) | O13—C28—C30 | 109.3 (2) |
O114—C128—C129 | 110.20 (18) | O14—C28—C30 | 108.6 (2) |
C130—C128—C129 | 112.7 (2) | C29—C28—C30 | 113.2 (2) |
C128—C130—H1301 | 110.4 | C28—C29—H292 | 110.3 |
C128—C130—H1302 | 109.9 | C28—C29—H291 | 109.3 |
H1301—C130—H1302 | 109.4 | H292—C29—H291 | 108.8 |
C128—C130—H1303 | 110.4 | C28—C29—H293 | 107.5 |
H1301—C130—H1303 | 108.7 | H292—C29—H293 | 108.6 |
H1302—C130—H1303 | 108.0 | H291—C29—H293 | 112.4 |
C128—C129—H1291 | 109.5 | C28—C30—H302 | 109.0 |
C128—C129—H1292 | 109.3 | C28—C30—H301 | 109.4 |
H1291—C129—H1292 | 109.3 | H302—C30—H301 | 109.2 |
C128—C129—H1293 | 109.3 | C28—C30—H303 | 108.9 |
H1291—C129—H1293 | 109.2 | H302—C30—H303 | 110.0 |
H1292—C129—H1293 | 110.3 | H301—C30—H303 | 110.4 |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H21···O109 | 0.90 | 1.80 | 2.664 (3) | 161 |
N102—H1021···O9 | 0.90 | 1.81 | 2.675 (3) | 162 |
O110—H1101···O109i | 0.81 | 2.69 | 3.348 (3) | 140 |
O10—H101···O11i | 0.83 | 2.50 | 3.187 (3) | 141 |
Symmetry code: (i) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C15H27NO7 |
Mr | 333.38 |
Crystal system, space group | Monoclinic, P21 |
Temperature (K) | 150 |
a, b, c (Å) | 5.7881 (2), 16.7077 (4), 17.8572 (5) |
β (°) | 99.1141 (8) |
V (Å3) | 1705.09 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.10 |
Crystal size (mm) | 0.40 × 0.10 × 0.08 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.96, 1.01 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 13496, 4000, 3474 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.032, 0.033, 1.09 |
No. of reflections | 3239 |
No. of parameters | 415 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.15 |
Computer programs: COLLECT (Nonius, 2001), DENZO/SCALEPACK (Otwinowski & Minor, 1997), SIR92 (Altomare et al., 1994), CRYSTALS (Betteridge et al., 2003), CAMERON (Watkin et al., 1996).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H21···O109 | 0.90 | 1.80 | 2.664 (3) | 161 |
N102—H1021···O9 | 0.90 | 1.81 | 2.675 (3) | 162 |
O110—H1101···O109i | 0.81 | 2.69 | 3.348 (3) | 140 |
O10—H101···O11i | 0.83 | 2.50 | 3.187 (3) | 141 |
Symmetry code: (i) x+1, y, z. |
References
Altomare, A., Cascarano, G., Giacovazzo, G., Guagliardi, A., Burla, M. C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. CrossRef Web of Science IUCr Journals Google Scholar
Betteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J. (2003). J. Appl. Cryst. 36, 1487. Web of Science CrossRef IUCr Journals Google Scholar
Hotchkiss, D. J., Jenkinson, S. F. & Fleet, G. W. J. (2008). Tetrahedron Lett. In preparation. Google Scholar
Hotchkiss, D. J., Soengas, R., Simone, M. I., van Ameijde, J., Hunter, S., Cowley, A. R. & Fleet, G. W. J. (2004). Tetrahedron Lett. 45, 9461–9464. Web of Science CrossRef CAS Google Scholar
Nonius (2001). COLLECT. Nonius BV, Delft, The Netherlands. Google Scholar
Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press. Google Scholar
Parker, S. G., Watkin, D. J., Simone, M. I. & Fleet, G. W. J. (2006). Acta Cryst. E62, o3961–o3963. Web of Science CSD CrossRef IUCr Journals Google Scholar
Prince, E. (1982). Mathematical Techniques in Crystallography and Materials Science. New York: Springer. Google Scholar
Risseeuw, M. D. P., Overhand, M., Fleet, G. W. J. & Simone, M. I. (2007). Tetrahedron Asymmetry, 18, 2001–2010. Web of Science CrossRef CAS Google Scholar
Simone, M., Fleet, G. W. J. & Watkin, D. J. (2007). Acta Cryst. E63, o799–o801. Web of Science CSD CrossRef IUCr Journals Google Scholar
Soengas, R., Izumori, K., Simone, M. I., Watkin, D. J., Skytte, U. P., Soetaert, W. & Fleet, G. W. J. (2005). Tetrahedron Lett. 46, 5755–5759. Web of Science CrossRef CAS Google Scholar
Watkin, D. (1994). Acta Cryst. A50, 411–437. CrossRef CAS Web of Science IUCr Journals Google Scholar
Watkin, D. J., Prout, C. K. & Pearce, L. J. (1996). CAMERON. Chemical Crystallography Laboratory, Oxford, England. Google Scholar
This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Sugar amino acids are a versatile class of conformationally biased building blocks, and have use as both glyco- and peptido-mimetics (Risseeuw et al., 2007). The Kiliani reaction on ketoses has been successfully utilized in the synthesis of branched carbohydrate building blocks (Hotchkiss et al., 2004; Soengas et al., 2005; Parker et al., 2006; Simone et al., 2007) to produce, for example, methyl or hydroxymethyl branched lactones. With Amadori products, 1-amino-1-deoxy-ketoses, as substrates, the Kiliani ascension should provide access to β-sugar amino acids. The reaction of 1-deoxy-1-(N,N-dimethylamino)-D-fructose, 2, an Amadori product readily available from D-glucose, 1, with sodium cyanide in water was found to give, after acetonide protection, the title compound, 3, as the major product. The stereochemistry at C-2 was unequivocally assigned by X-ray crystallography (Fig. 2) and the absolute stereochemistry was determined by the use of D-glucose as the starting material.
The asymmetric unit contains of two crystallographically distinct molecules which are related by a pseudo-2-fold rotation axis. These are similar in geometry with the exception of one of the isopropylidene rings: in the first molecule the atoms C20, O13, O14 and C28 are approximately coplanar while C21 is displaced from this plane, whereas in the second molecule C120, C121, O113 and C128 are approximately coplanar while O114 is displaced. The r.m.s. bond length deviation for the two molecules, excluding hydrogen atoms, is 0.007 Å.
Hydrogen bonding links molecules to form infinite chains running parallel to the crystallographic a axis (Fig. 3). There are two weak hydrogen bonds between the layers and two strong hydrogen bonds linking the two molecules in the asymmetric unit (Fig. 4).