

Supporting information
![]() | Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044911/cf2137sup1.cif |
![]() | Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044911/cf2137Isup2.hkl |
CCDC reference: 663810
2-O-(4,4'-Dimethylbenzhydryl)-L-erythronolactone was recrystallized by vapour diffusion of hexane into ethyl acetate: m.p. 425–427 K; [α]D21 -51.7 (c, 1.08 in chloroform).
In the absence of significant anomalous scattering, Friedel pairs were merged and the absolute configuration was assigned on the basis of the starting material.
The relatively large ratio of minimum to maximum corrections applied in the multiscan process (1:1.18) reflect changes in the illuminated volume of the crystal. Changes in illuminated volume were kept to a minimum, and were taken into account (Görbitz, 1999) by the multi-scan inter-frame scaling (DENZO/SCALEPACK, Otwinowski & Minor, 1997).
The 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 and 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.
Carbohydrates provide excellent starting materials for the synthesis of small chiral molecules (Collins & Ferrier, 1995). They are relatively inexpensive and provide an almost boundless pool of chiral building blocks (Draths et al., 1992). L-Erythronolactone 1, readily available from D-arabinose (Humphlett, 1967), is an underused carbohydrate synthon due to the difficulty in differentiating between the two secondary hydroxyl groups.
Diazodiphenylmethane has been found to be a useful protecting group in the synthesis of methyl 2,3,6-tri-O-methyl-[α]-D-glucopyranoside and kojibiose octa-acetate (Jackson et al., 1982), and monoalkylations of vicinal diols have been achieved with this reagent and other diaryldiazoalkanes in the presence of catalytic amounts of tin(II) chloride with high regioselectivities (Petursson & Webber, 1982; Petursson, 2001, 2003).
The reaction of L-erythronolactone with diazo[bis(4-methylphenyl)]methane and a catalytic amount of tin(II) chloride in 1,2-dimethoxyethane gave a 5:1 mixture of mono-protected lactones 2 and 3 (Fig. 1). The crystal structure has firmly established that the major product is the title compound, 2 (Fig. 2). The crystal structure consists of alternating hydrogen-bonded chains of molecules lying perpendicular to the bc plane (Fig. 3).
For related literature, see: Humphlett (1967); Jackson et al. (1982); Petursson & Webber (1982); Petursson (2001, 2003); Collins & Ferrier (1995); Draths et al. (1992); Görbitz (1999).
Data collection: COLLECT (Nonius, 2001); cell refinement: 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).
C19H20O4 | Dx = 1.268 Mg m−3 |
Mr = 312.37 | Mo Kα radiation, λ = 0.71073 Å |
Orthorhombic, P212121 | Cell parameters from 1832 reflections |
a = 6.1276 (2) Å | θ = 5–27° |
b = 8.8248 (3) Å | µ = 0.09 mm−1 |
c = 30.2629 (10) Å | T = 150 K |
V = 1636.46 (9) Å3 | Needle, colourless |
Z = 4 | 0.50 × 0.10 × 0.10 mm |
F(000) = 664 |
Nonius KappaCCD diffractometer | 1323 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.086 |
ω scans | θmax = 27.5°, θmin = 5.2° |
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) | h = −7→7 |
Tmin = 0.84, Tmax = 0.99 | k = −11→11 |
7163 measured reflections | l = −37→38 |
2112 independent reflections |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.059 | H-atom parameters constrained |
wR(F2) = 0.171 | w = 1/[σ2(F2) + (0.1P)2]
, where P = (max(Fo2,0) + 2Fc2)/3 |
S = 0.93 | (Δ/σ)max = 0.000110 |
2112 reflections | Δρmax = 0.39 e Å−3 |
208 parameters | Δρmin = −0.39 e Å−3 |
0 restraints |
C19H20O4 | V = 1636.46 (9) Å3 |
Mr = 312.37 | Z = 4 |
Orthorhombic, P212121 | Mo Kα radiation |
a = 6.1276 (2) Å | µ = 0.09 mm−1 |
b = 8.8248 (3) Å | T = 150 K |
c = 30.2629 (10) Å | 0.50 × 0.10 × 0.10 mm |
Nonius KappaCCD diffractometer | 2112 independent reflections |
Absorption correction: multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) | 1323 reflections with I > 2σ(I) |
Tmin = 0.84, Tmax = 0.99 | Rint = 0.086 |
7163 measured reflections |
R[F2 > 2σ(F2)] = 0.059 | 0 restraints |
wR(F2) = 0.171 | H-atom parameters constrained |
S = 0.93 | Δρmax = 0.39 e Å−3 |
2112 reflections | Δρmin = −0.39 e Å−3 |
208 parameters |
x | y | z | Uiso*/Ueq | ||
O1 | 0.5621 (5) | 0.7497 (3) | 0.16641 (6) | 0.0368 | |
C2 | 0.5141 (7) | 0.6595 (4) | 0.12785 (10) | 0.0360 | |
C3 | 0.6524 (7) | 0.5171 (4) | 0.12688 (10) | 0.0328 | |
C4 | 0.8599 (8) | 0.5137 (4) | 0.14619 (10) | 0.0381 | |
C5 | 0.9777 (8) | 0.3806 (5) | 0.14738 (11) | 0.0406 | |
C6 | 0.8997 (8) | 0.2478 (5) | 0.12948 (11) | 0.0423 | |
C7 | 0.6980 (8) | 0.2533 (5) | 0.10875 (12) | 0.0461 | |
C8 | 0.5765 (8) | 0.3839 (4) | 0.10784 (10) | 0.0380 | |
C9 | 1.0239 (11) | 0.1014 (5) | 0.13336 (14) | 0.0682 | |
C10 | 0.5396 (7) | 0.7615 (4) | 0.08805 (10) | 0.0360 | |
C11 | 0.7307 (8) | 0.7685 (5) | 0.06273 (12) | 0.0447 | |
C12 | 0.7456 (9) | 0.8691 (5) | 0.02763 (12) | 0.0476 | |
C13 | 0.5725 (8) | 0.9631 (5) | 0.01651 (11) | 0.0424 | |
C14 | 0.3827 (8) | 0.9546 (5) | 0.04116 (11) | 0.0446 | |
C15 | 0.3677 (8) | 0.8529 (5) | 0.07647 (11) | 0.0422 | |
C16 | 0.5911 (10) | 1.0723 (6) | −0.02186 (13) | 0.0653 | |
C17 | 0.4910 (7) | 0.6830 (4) | 0.20603 (10) | 0.0354 | |
C18 | 0.2803 (7) | 0.7510 (5) | 0.22240 (11) | 0.0372 | |
O19 | 0.2760 (5) | 0.7464 (3) | 0.26658 (7) | 0.0452 | |
C20 | 0.4842 (8) | 0.6878 (5) | 0.28307 (11) | 0.0488 | |
C21 | 0.6449 (7) | 0.7073 (5) | 0.24494 (12) | 0.0392 | |
O22 | 0.7273 (5) | 0.8564 (3) | 0.24595 (8) | 0.0425 | |
O23 | 0.1313 (5) | 0.8012 (3) | 0.20124 (8) | 0.0481 | |
H21 | 0.3591 | 0.6243 | 0.1266 | 0.0485* | |
H41 | 0.9144 | 0.6059 | 0.1587 | 0.0493* | |
H51 | 1.1210 | 0.3779 | 0.1629 | 0.0504* | |
H71 | 0.6433 | 0.1650 | 0.0941 | 0.0580* | |
H81 | 0.4389 | 0.3839 | 0.0941 | 0.0458* | |
H91 | 0.9516 | 0.0236 | 0.1167 | 0.1067* | |
H92 | 1.0233 | 0.0731 | 0.1638 | 0.1061* | |
H93 | 1.1723 | 0.1170 | 0.1245 | 0.1064* | |
H111 | 0.8500 | 0.7011 | 0.0690 | 0.0541* | |
H121 | 0.8764 | 0.8725 | 0.0102 | 0.0612* | |
H141 | 0.2599 | 1.0180 | 0.0336 | 0.0573* | |
H151 | 0.2375 | 0.8467 | 0.0924 | 0.0525* | |
H161 | 0.4540 | 1.1194 | −0.0262 | 0.1014* | |
H162 | 0.7021 | 1.1475 | −0.0148 | 0.1017* | |
H163 | 0.6272 | 1.0160 | −0.0482 | 0.1013* | |
H171 | 0.4638 | 0.5726 | 0.2016 | 0.0455* | |
H201 | 0.5259 | 0.7483 | 0.3091 | 0.0600* | |
H202 | 0.4712 | 0.5830 | 0.2925 | 0.0609* | |
H211 | 0.7611 | 0.6306 | 0.2456 | 0.0579* | |
H26 | 0.8375 | 0.8918 | 0.2326 | 0.0714* |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.0501 (18) | 0.0382 (13) | 0.0222 (11) | −0.0038 (15) | 0.0037 (11) | −0.0011 (10) |
C2 | 0.036 (2) | 0.045 (2) | 0.0275 (16) | −0.002 (2) | −0.0028 (17) | −0.0065 (15) |
C3 | 0.035 (2) | 0.0386 (19) | 0.0252 (16) | −0.0005 (19) | −0.0009 (16) | 0.0027 (14) |
C4 | 0.041 (3) | 0.039 (2) | 0.0348 (18) | −0.001 (2) | −0.0005 (18) | −0.0061 (15) |
C5 | 0.040 (3) | 0.049 (2) | 0.0331 (18) | 0.006 (2) | −0.0016 (18) | 0.0042 (16) |
C6 | 0.056 (3) | 0.038 (2) | 0.0336 (18) | 0.008 (2) | 0.0120 (19) | 0.0021 (17) |
C7 | 0.059 (3) | 0.042 (2) | 0.037 (2) | −0.006 (3) | 0.008 (2) | −0.0102 (17) |
C8 | 0.046 (3) | 0.044 (2) | 0.0242 (17) | −0.005 (2) | −0.0048 (17) | −0.0050 (14) |
C9 | 0.074 (4) | 0.049 (3) | 0.081 (3) | 0.015 (3) | 0.012 (3) | −0.004 (2) |
C10 | 0.039 (3) | 0.039 (2) | 0.0298 (17) | 0.004 (2) | 0.0001 (16) | −0.0011 (15) |
C11 | 0.045 (3) | 0.052 (2) | 0.0367 (19) | 0.004 (3) | 0.0018 (18) | 0.0042 (18) |
C12 | 0.047 (3) | 0.057 (3) | 0.040 (2) | −0.002 (3) | 0.0105 (19) | 0.0012 (19) |
C13 | 0.051 (3) | 0.046 (2) | 0.0302 (17) | −0.001 (2) | −0.0081 (19) | 0.0012 (16) |
C14 | 0.051 (3) | 0.042 (2) | 0.0409 (19) | 0.002 (3) | −0.003 (2) | 0.0048 (17) |
C15 | 0.043 (3) | 0.045 (2) | 0.038 (2) | 0.003 (2) | 0.0085 (19) | −0.0007 (17) |
C16 | 0.075 (4) | 0.068 (3) | 0.053 (2) | −0.008 (3) | 0.001 (3) | 0.017 (2) |
C17 | 0.040 (3) | 0.043 (2) | 0.0232 (16) | 0.001 (2) | 0.0030 (16) | −0.0016 (14) |
C18 | 0.036 (3) | 0.048 (2) | 0.0275 (18) | 0.000 (2) | 0.0035 (16) | −0.0025 (18) |
O19 | 0.045 (2) | 0.0615 (19) | 0.0292 (13) | 0.001 (2) | 0.0068 (11) | −0.0063 (12) |
C20 | 0.050 (3) | 0.070 (3) | 0.0267 (18) | −0.006 (3) | 0.0027 (19) | −0.0018 (17) |
C21 | 0.042 (3) | 0.046 (2) | 0.0296 (17) | 0.003 (2) | 0.0038 (17) | 0.0032 (15) |
O22 | 0.0353 (17) | 0.0492 (17) | 0.0431 (14) | −0.0052 (15) | 0.0026 (13) | −0.0066 (12) |
O23 | 0.0347 (19) | 0.0587 (19) | 0.0510 (15) | 0.0003 (17) | 0.0023 (14) | −0.0021 (13) |
O1—C2 | 1.443 (4) | C12—C13 | 1.388 (6) |
O1—C17 | 1.405 (4) | C12—H121 | 0.960 |
C2—C3 | 1.516 (5) | C13—C14 | 1.384 (6) |
C2—C10 | 1.512 (5) | C13—C16 | 1.513 (6) |
C2—H21 | 1.000 | C14—C15 | 1.398 (5) |
C3—C4 | 1.399 (6) | C14—H141 | 0.965 |
C3—C8 | 1.389 (5) | C15—H151 | 0.934 |
C4—C5 | 1.379 (5) | C16—H161 | 0.946 |
C4—H41 | 0.958 | C16—H162 | 0.974 |
C5—C6 | 1.377 (6) | C16—H163 | 0.965 |
C5—H51 | 0.995 | C17—C18 | 1.507 (5) |
C6—C7 | 1.387 (6) | C17—C21 | 1.524 (5) |
C6—C9 | 1.504 (6) | C17—H171 | 0.997 |
C7—C8 | 1.373 (6) | C18—O19 | 1.338 (4) |
C7—H71 | 0.957 | C18—O23 | 1.200 (5) |
C8—H81 | 0.940 | O19—C20 | 1.465 (5) |
C9—H91 | 0.961 | C20—C21 | 1.527 (6) |
C9—H92 | 0.953 | C20—H201 | 0.985 |
C9—H93 | 0.958 | C20—H202 | 0.971 |
C10—C11 | 1.401 (5) | C21—O22 | 1.409 (5) |
C10—C15 | 1.372 (6) | C21—H211 | 0.982 |
C11—C12 | 1.388 (5) | O22—H26 | 0.847 |
C11—H111 | 0.961 | ||
C2—O1—C17 | 113.3 (3) | C13—C12—H121 | 119.1 |
O1—C2—C3 | 111.0 (3) | C12—C13—C14 | 118.6 (3) |
O1—C2—C10 | 107.1 (3) | C12—C13—C16 | 120.6 (4) |
C3—C2—C10 | 114.9 (3) | C14—C13—C16 | 120.8 (4) |
O1—C2—H21 | 113.3 | C13—C14—C15 | 120.2 (4) |
C3—C2—H21 | 105.8 | C13—C14—H141 | 119.8 |
C10—C2—H21 | 104.7 | C15—C14—H141 | 120.1 |
C2—C3—C4 | 121.2 (3) | C14—C15—C10 | 121.4 (4) |
C2—C3—C8 | 121.4 (4) | C14—C15—H151 | 119.3 |
C4—C3—C8 | 117.3 (4) | C10—C15—H151 | 119.3 |
C3—C4—C5 | 120.3 (4) | C13—C16—H161 | 108.6 |
C3—C4—H41 | 117.7 | C13—C16—H162 | 108.5 |
C5—C4—H41 | 122.0 | H161—C16—H162 | 110.6 |
C4—C5—C6 | 122.2 (4) | C13—C16—H163 | 108.9 |
C4—C5—H51 | 119.7 | H161—C16—H163 | 108.4 |
C6—C5—H51 | 118.1 | H162—C16—H163 | 111.8 |
C5—C6—C7 | 117.3 (4) | O1—C17—C18 | 112.3 (3) |
C5—C6—C9 | 121.7 (4) | O1—C17—C21 | 114.1 (3) |
C7—C6—C9 | 121.1 (4) | C18—C17—C21 | 102.7 (3) |
C6—C7—C8 | 121.4 (4) | O1—C17—H171 | 110.2 |
C6—C7—H71 | 119.6 | C18—C17—H171 | 106.9 |
C8—C7—H71 | 119.0 | C21—C17—H171 | 110.2 |
C3—C8—C7 | 121.4 (4) | C17—C18—O19 | 109.5 (3) |
C3—C8—H81 | 119.0 | C17—C18—O23 | 128.6 (3) |
C7—C8—H81 | 119.7 | O19—C18—O23 | 122.0 (4) |
C6—C9—H91 | 109.8 | C18—O19—C20 | 109.5 (3) |
C6—C9—H92 | 107.4 | O19—C20—C21 | 105.3 (3) |
H91—C9—H92 | 108.6 | O19—C20—H201 | 107.8 |
C6—C9—H93 | 109.6 | C21—C20—H201 | 112.1 |
H91—C9—H93 | 113.2 | O19—C20—H202 | 111.4 |
H92—C9—H93 | 108.1 | C21—C20—H202 | 112.5 |
C2—C10—C11 | 123.3 (4) | H201—C20—H202 | 107.7 |
C2—C10—C15 | 118.3 (3) | C20—C21—C17 | 99.7 (4) |
C11—C10—C15 | 118.4 (3) | C20—C21—O22 | 108.7 (3) |
C10—C11—C12 | 120.1 (4) | C17—C21—O22 | 111.7 (3) |
C10—C11—H111 | 120.0 | C20—C21—H211 | 111.9 |
C12—C11—H111 | 119.8 | C17—C21—H211 | 111.6 |
C11—C12—C13 | 121.2 (4) | O22—C21—H211 | 112.5 |
C11—C12—H121 | 119.7 | C21—O22—H26 | 128.3 |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H41···O23i | 0.96 | 2.53 | 3.461 (6) | 165 |
O22—H26···O23i | 0.85 | 2.19 | 2.863 (6) | 137 |
Symmetry code: (i) x+1, y, z. |
Experimental details
Crystal data | |
Chemical formula | C19H20O4 |
Mr | 312.37 |
Crystal system, space group | Orthorhombic, P212121 |
Temperature (K) | 150 |
a, b, c (Å) | 6.1276 (2), 8.8248 (3), 30.2629 (10) |
V (Å3) | 1636.46 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.50 × 0.10 × 0.10 |
Data collection | |
Diffractometer | Nonius KappaCCD |
Absorption correction | Multi-scan (DENZO/SCALEPACK; Otwinowski & Minor, 1997) |
Tmin, Tmax | 0.84, 0.99 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7163, 2112, 1323 |
Rint | 0.086 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.059, 0.171, 0.93 |
No. of reflections | 2112 |
No. of parameters | 208 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.39, −0.39 |
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 |
O22—H26···O23i | 0.85 | 2.19 | 2.863 (6) | 137 |
Symmetry code: (i) x+1, y, z. |
Carbohydrates provide excellent starting materials for the synthesis of small chiral molecules (Collins & Ferrier, 1995). They are relatively inexpensive and provide an almost boundless pool of chiral building blocks (Draths et al., 1992). L-Erythronolactone 1, readily available from D-arabinose (Humphlett, 1967), is an underused carbohydrate synthon due to the difficulty in differentiating between the two secondary hydroxyl groups.
Diazodiphenylmethane has been found to be a useful protecting group in the synthesis of methyl 2,3,6-tri-O-methyl-[α]-D-glucopyranoside and kojibiose octa-acetate (Jackson et al., 1982), and monoalkylations of vicinal diols have been achieved with this reagent and other diaryldiazoalkanes in the presence of catalytic amounts of tin(II) chloride with high regioselectivities (Petursson & Webber, 1982; Petursson, 2001, 2003).
The reaction of L-erythronolactone with diazo[bis(4-methylphenyl)]methane and a catalytic amount of tin(II) chloride in 1,2-dimethoxyethane gave a 5:1 mixture of mono-protected lactones 2 and 3 (Fig. 1). The crystal structure has firmly established that the major product is the title compound, 2 (Fig. 2). The crystal structure consists of alternating hydrogen-bonded chains of molecules lying perpendicular to the bc plane (Fig. 3).