1-Dibenzylamino-1-de-oxy-4,5-O-isopropyl-idene-β-d-fructopyran-ose.

The title compound C(23)H(29)NO(5), synthesized by the Amadori rearrangement of α-d-glucose with dibenzyl-amine and the ketalization, is shown to be a β-anomer. The fructopyran-ose ring adopts a chair conformation. The two benzene rings form a dihedral angle of 68.9 (1)°. In the crystal, non-classical inter-molecular C-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional network.

Related literature

For details of the synthesis of the title compound and the related ketone catalyst for asymmetric epoxidation, see: Shu et al. (2003 ▶); Tian et al. (2000 ▶, 2002 ▶).

Experimental

Crystal data

C23H29NO5

M = 399.47

Orthorhombic,

a = 8.328 (3) Å

b = 15.635 (5) Å

c = 16.547 (5) Å

V = 2154.6 (12) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 293 K

0.32 × 0.26 × 0.18 mm

Data collection

Bruker SMART APEX CCD diffractometer

8591 measured reflections

3746 independent reflections

3078 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.099

S = 0.99

3746 reflections

264 parameters

12 restraints

H-atom parameters constrained

Δρmax = 0.16 e Å−3

Δρmin = −0.14 e Å−3

Data collection: SMART (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; 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.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810053973/rk2247sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810053973/rk2247Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C23H29NO5	Dx = 1.232 Mg m−3
Mr = 399.47	Melting point: 363 K
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2101 reflections
a = 8.328 (3) Å	θ = 2.5–22.9°
b = 15.635 (5) Å	µ = 0.09 mm−1
c = 16.547 (5) Å	T = 293 K
V = 2154.6 (12) Å3	Block, colourless
Z = 4	0.32 × 0.26 × 0.18 mm
F(000) = 856

Bruker SMART APEX CCD diffractometer	3078 reflections with I > 2σ(I)
Radiation source: fine–focus sealed tube	Rint = 0.029
graphite	θmax = 25.0°, θmin = 2.5°
φ– and ω–scans	h = −9→9
8591 measured reflections	k = −12→18
3746 independent reflections	l = −19→19

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) = 0.099	w = 1/[σ2(Fo2) + (0.0586P)2] where P = (Fo2 + 2Fc2)/3
S = 0.99	(Δ/σ)max < 0.001
3746 reflections	Δρmax = 0.16 e Å−3
264 parameters	Δρmin = −0.14 e Å−3
12 restraints	Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0109 (15)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R–factor wR and goodness of fit S are based on F2, conventional R–factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R–factors(gt) etc. and is not relevant to the choice of reflections for refinement. R–factors based on F2 are statistically about twice as large as those based on F, and R–factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
N1	0.45371 (19)	−0.03531 (9)	−0.03276 (9)	0.0445 (4)
O1	0.26735 (16)	0.12669 (8)	0.01447 (7)	0.0462 (3)
O2	0.44619 (18)	0.05470 (9)	0.09987 (8)	0.0570 (4)
H2A	0.5176	0.0562	0.0658	0.086*
O3	0.1840 (3)	−0.02563 (10)	0.17613 (11)	0.0803 (5)
H3	0.2784	−0.0405	0.1776	0.120*
O4	0.03036 (19)	0.23207 (9)	0.11486 (7)	0.0552 (4)
O5	0.02593 (19)	0.14018 (9)	0.22165 (8)	0.0597 (4)
C1	0.2928 (3)	0.20454 (12)	0.05737 (11)	0.0531 (5)
H1A	0.2674	0.2522	0.0221	0.064*
H1B	0.4054	0.2088	0.0718	0.064*
C2	0.1933 (3)	0.21137 (12)	0.13278 (11)	0.0496 (5)
H2B	0.2389	0.2553	0.1682	0.059*
C3	0.1735 (3)	0.12850 (13)	0.17977 (11)	0.0488 (5)
H3B	0.2610	0.1232	0.2190	0.059*
C4	0.1688 (3)	0.04895 (12)	0.12720 (11)	0.0494 (5)
H4A	0.0637	0.0469	0.1007	0.059*
C5	0.2971 (2)	0.05151 (12)	0.06144 (10)	0.0430 (4)
C6	0.2938 (2)	−0.02364 (12)	0.00288 (11)	0.0468 (5)
H6A	0.2621	−0.0752	0.0313	0.056*
H6B	0.2159	−0.0129	−0.0395	0.056*
C7	0.4851 (3)	−0.12466 (12)	−0.05526 (12)	0.0552 (5)
H7A	0.5860	−0.1272	−0.0844	0.066*
H7B	0.4012	−0.1435	−0.0918	0.066*
C8	0.4931 (3)	−0.18588 (12)	0.01473 (13)	0.0530 (5)
C9	0.5592 (4)	−0.16474 (16)	0.08772 (15)	0.0766 (7)
H9A	0.5991	−0.1098	0.0956	0.092*
C10	0.5678 (4)	−0.2241 (2)	0.15046 (17)	0.0973 (10)
H10A	0.6114	−0.2084	0.2000	0.117*
C11	0.5121 (4)	−0.30535 (19)	0.1390 (2)	0.0940 (10)
H11A	0.5185	−0.3452	0.1806	0.113*
C12	0.4479 (4)	−0.32744 (19)	0.0676 (3)	0.0989 (10)
H12A	0.4106	−0.3829	0.0598	0.119*
C13	0.4368 (3)	−0.26813 (14)	0.00508 (19)	0.0782 (7)
H13A	0.3909	−0.2842	−0.0438	0.094*
C14	0.4789 (2)	0.02062 (13)	−0.10350 (11)	0.0487 (5)
H14A	0.4304	0.0759	−0.0929	0.058*
H14B	0.4248	−0.0041	−0.1499	0.058*
C15	0.6535 (2)	0.03325 (11)	−0.12364 (10)	0.0422 (4)
C16	0.7148 (3)	0.01268 (14)	−0.19830 (12)	0.0573 (5)
H16A	0.6475	−0.0112	−0.2371	0.069*
C17	0.8741 (3)	0.02674 (16)	−0.21685 (14)	0.0697 (7)
H17A	0.9137	0.0117	−0.2674	0.084*
C18	0.9742 (3)	0.06300 (15)	−0.16054 (15)	0.0674 (6)
H18A	1.0814	0.0729	−0.1731	0.081*
C19	0.9159 (3)	0.08463 (14)	−0.08581 (15)	0.0604 (6)
H19A	0.9832	0.1094	−0.0476	0.072*
C20	0.7577 (3)	0.06950 (12)	−0.06777 (12)	0.0525 (5)
H20A	0.7192	0.0839	−0.0168	0.063*
C21	−0.0606 (3)	0.21023 (14)	0.18498 (12)	0.0547 (5)
C22	−0.0670 (4)	0.28284 (16)	0.24500 (15)	0.0808 (8)
H22A	0.0402	0.2995	0.2592	0.121*
H22B	−0.1232	0.2646	0.2926	0.121*
H22C	−0.1221	0.3306	0.2213	0.121*
C23	−0.2231 (3)	0.1807 (2)	0.15849 (16)	0.0861 (8)
H23A	−0.2117	0.1346	0.1207	0.129*
H23B	−0.2791	0.2273	0.1332	0.129*
H23C	−0.2829	0.1614	0.2046	0.129*

	U11	U22	U33	U12	U13	U23
N1	0.0465 (10)	0.0434 (8)	0.0437 (8)	0.0012 (7)	0.0014 (7)	0.0021 (7)
O1	0.0531 (8)	0.0446 (7)	0.0408 (6)	−0.0049 (6)	0.0027 (6)	0.0049 (6)
O2	0.0469 (8)	0.0727 (9)	0.0514 (7)	−0.0011 (7)	−0.0076 (6)	0.0009 (7)
O3	0.1109 (15)	0.0558 (9)	0.0741 (10)	0.0149 (9)	0.0334 (11)	0.0294 (8)
O4	0.0653 (10)	0.0561 (8)	0.0442 (7)	0.0055 (7)	0.0080 (7)	0.0095 (6)
O5	0.0731 (10)	0.0584 (9)	0.0475 (7)	0.0065 (8)	0.0185 (7)	0.0122 (7)
C1	0.0606 (14)	0.0458 (10)	0.0528 (11)	−0.0090 (9)	0.0062 (10)	0.0019 (9)
C2	0.0558 (14)	0.0499 (11)	0.0430 (10)	−0.0093 (9)	0.0012 (10)	−0.0005 (9)
C3	0.0522 (12)	0.0571 (11)	0.0370 (9)	−0.0009 (10)	0.0017 (9)	0.0052 (9)
C4	0.0547 (13)	0.0472 (10)	0.0463 (10)	0.0015 (9)	0.0048 (10)	0.0144 (9)
C5	0.0411 (11)	0.0450 (9)	0.0431 (9)	−0.0026 (8)	−0.0022 (8)	0.0054 (8)
C6	0.0438 (12)	0.0464 (10)	0.0501 (10)	−0.0039 (8)	−0.0001 (9)	0.0051 (9)
C7	0.0651 (14)	0.0494 (11)	0.0511 (10)	0.0006 (10)	0.0012 (10)	−0.0058 (9)
C8	0.0459 (12)	0.0477 (11)	0.0655 (13)	0.0076 (9)	0.0075 (10)	0.0001 (10)
C9	0.105 (2)	0.0565 (13)	0.0679 (14)	0.0125 (14)	−0.0144 (15)	0.0049 (12)
C10	0.129 (3)	0.090 (2)	0.0731 (16)	0.0303 (19)	−0.0086 (17)	0.0177 (16)
C11	0.093 (2)	0.0794 (19)	0.110 (2)	0.0139 (16)	0.014 (2)	0.0413 (18)
C12	0.080 (2)	0.0638 (16)	0.153 (3)	−0.0102 (15)	0.000 (2)	0.0341 (19)
C13	0.0732 (17)	0.0566 (14)	0.1049 (19)	−0.0096 (12)	−0.0098 (15)	0.0108 (14)
C14	0.0523 (13)	0.0525 (10)	0.0413 (9)	−0.0004 (10)	−0.0045 (9)	0.0049 (9)
C15	0.0498 (12)	0.0368 (9)	0.0400 (9)	0.0008 (8)	−0.0027 (9)	0.0020 (8)
C16	0.0625 (15)	0.0628 (12)	0.0466 (11)	−0.0070 (11)	0.0016 (10)	−0.0054 (10)
C17	0.0740 (17)	0.0777 (16)	0.0575 (12)	−0.0052 (13)	0.0190 (12)	−0.0024 (13)
C18	0.0500 (14)	0.0664 (14)	0.0857 (16)	0.0005 (11)	0.0078 (13)	0.0138 (13)
C19	0.0523 (14)	0.0537 (12)	0.0752 (15)	−0.0066 (10)	−0.0172 (12)	0.0066 (11)
C20	0.0599 (14)	0.0515 (11)	0.0461 (10)	0.0015 (10)	−0.0060 (10)	−0.0040 (9)
C21	0.0632 (14)	0.0564 (11)	0.0444 (10)	0.0050 (10)	0.0082 (10)	0.0064 (9)
C22	0.112 (2)	0.0641 (14)	0.0663 (14)	0.0090 (15)	0.0213 (16)	−0.0049 (13)
C23	0.0639 (18)	0.123 (2)	0.0719 (15)	−0.0073 (16)	0.0027 (14)	0.0065 (16)

N1—C6	1.468 (2)	C9—H9A	0.9300
N1—C7	1.469 (2)	C10—C11	1.366 (5)
N1—C14	1.476 (2)	C10—H10A	0.9300
O1—C1	1.425 (2)	C11—C12	1.343 (5)
O1—C5	1.431 (2)	C11—H11A	0.9300
O2—C5	1.396 (2)	C12—C13	1.392 (4)
O2—H2A	0.8200	C12—H12A	0.9300
O3—C4	1.425 (2)	C13—H13A	0.9300
O3—H3	0.8200	C14—C15	1.505 (3)
O4—C2	1.426 (3)	C14—H14A	0.9700
O4—C21	1.427 (2)	C14—H14B	0.9700
O5—C3	1.423 (3)	C15—C16	1.375 (3)
O5—C21	1.445 (2)	C15—C20	1.389 (3)
C1—C2	1.502 (3)	C16—C17	1.380 (3)
C1—H1A	0.9700	C16—H16A	0.9300
C1—H1B	0.9700	C17—C18	1.373 (3)
C2—C3	1.520 (3)	C17—H17A	0.9300
C2—H2B	0.9800	C18—C19	1.371 (3)
C3—C4	1.518 (3)	C18—H18A	0.9300
C3—H3B	0.9800	C19—C20	1.372 (3)
C4—C5	1.526 (3)	C19—H19A	0.9300
C4—H4A	0.9800	C20—H20A	0.9300
C5—C6	1.523 (3)	C21—C23	1.495 (4)
C6—H6A	0.9700	C21—C22	1.509 (3)
C6—H6B	0.9700	C22—H22A	0.9600
C7—C8	1.504 (3)	C22—H22B	0.9600
C7—H7A	0.9700	C22—H22C	0.9600
C7—H7B	0.9700	C23—H23A	0.9600
C8—C9	1.368 (3)	C23—H23B	0.9600
C8—C13	1.378 (3)	C23—H23C	0.9600
C9—C10	1.394 (4)
C6—N1—C7	112.42 (15)	C10—C9—H9A	119.4
C6—N1—C14	111.94 (15)	C11—C10—C9	119.9 (3)
C7—N1—C14	109.70 (15)	C11—C10—H10A	120.0
C1—O1—C5	113.91 (13)	C9—C10—H10A	120.0
C5—O2—H2A	109.5	C12—C11—C10	119.8 (3)
C4—O3—H3	109.5	C12—C11—H11A	120.1
C2—O4—C21	106.38 (15)	C10—C11—H11A	120.1
C3—O5—C21	108.89 (14)	C11—C12—C13	120.6 (3)
O1—C1—C2	113.12 (16)	C11—C12—H12A	119.7
O1—C1—H1A	109.0	C13—C12—H12A	119.7
C2—C1—H1A	109.0	C8—C13—C12	120.9 (3)
O1—C1—H1B	109.0	C8—C13—H13A	119.6
C2—C1—H1B	109.0	C12—C13—H13A	119.6
H1A—C1—H1B	107.8	N1—C14—C15	112.98 (15)
O4—C2—C1	111.62 (16)	N1—C14—H14A	109.0
O4—C2—C3	101.33 (16)	C15—C14—H14A	109.0
C1—C2—C3	115.10 (17)	N1—C14—H14B	109.0
O4—C2—H2B	109.5	C15—C14—H14B	109.0
C1—C2—H2B	109.5	H14A—C14—H14B	107.8
C3—C2—H2B	109.5	C16—C15—C20	117.5 (2)
O5—C3—C4	111.21 (17)	C16—C15—C14	121.80 (18)
O5—C3—C2	103.50 (16)	C20—C15—C14	120.65 (17)
C4—C3—C2	114.08 (14)	C15—C16—C17	121.3 (2)
O5—C3—H3B	109.3	C15—C16—H16A	119.3
C4—C3—H3B	109.3	C17—C16—H16A	119.3
C2—C3—H3B	109.3	C18—C17—C16	119.9 (2)
O3—C4—C3	110.03 (15)	C18—C17—H17A	120.0
O3—C4—C5	111.37 (16)	C16—C17—H17A	120.0
C3—C4—C5	111.65 (16)	C19—C18—C17	120.0 (2)
O3—C4—H4A	107.9	C19—C18—H18A	120.0
C3—C4—H4A	107.9	C17—C18—H18A	120.0
C5—C4—H4A	107.9	C18—C19—C20	119.6 (2)
O2—C5—O1	111.86 (14)	C18—C19—H19A	120.2
O2—C5—C6	109.49 (15)	C20—C19—H19A	120.2
O1—C5—C6	106.55 (13)	C19—C20—C15	121.7 (2)
O2—C5—C4	107.41 (15)	C19—C20—H20A	119.1
O1—C5—C4	106.71 (15)	C15—C20—H20A	119.1
C6—C5—C4	114.87 (16)	O4—C21—O5	104.94 (17)
N1—C6—C5	109.56 (15)	O4—C21—C23	108.43 (18)
N1—C6—H6A	109.8	O5—C21—C23	109.9 (2)
C5—C6—H6A	109.8	O4—C21—C22	111.94 (18)
N1—C6—H6B	109.8	O5—C21—C22	108.14 (18)
C5—C6—H6B	109.8	C23—C21—C22	113.1 (2)
H6A—C6—H6B	108.2	C21—C22—H22A	109.5
N1—C7—C8	114.70 (15)	C21—C22—H22B	109.5
N1—C7—H7A	108.6	H22A—C22—H22B	109.5
C8—C7—H7A	108.6	C21—C22—H22C	109.5
N1—C7—H7B	108.6	H22A—C22—H22C	109.5
C8—C7—H7B	108.6	H22B—C22—H22C	109.5
H7A—C7—H7B	107.6	C21—C23—H23A	109.5
C9—C8—C13	117.7 (2)	C21—C23—H23B	109.5
C9—C8—C7	122.96 (19)	H23A—C23—H23B	109.5
C13—C8—C7	119.3 (2)	C21—C23—H23C	109.5
C8—C9—C10	121.2 (3)	H23A—C23—H23C	109.5
C8—C9—H9A	119.4	H23B—C23—H23C	109.5
C3—C2—C1—O1	37.9 (3)	C4—C3—C2—C1	−32.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16A···O5i	0.93	2.57	3.389 (3)	147
C17—H17A···O2ii	0.93	2.70	3.614 (3)	170
C19—H19A···O1iii	0.93	2.59	3.428 (3)	150

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16A⋯O5i	0.93	2.57	3.389 (3)	147
C17—H17A⋯O2ii	0.93	2.70	3.614 (3)	170
C19—H19A⋯O1iii	0.93	2.59	3.428 (3)	150

Symmetry codes: (i) ; (ii) ; (iii) .