1,5-Anhydro-2,3-O-isopropyl­idene-l-lyxofuran­ose [(1S,4S,5S,6R)-5,6-O-isopropylidene-2,7-dioxabicyclo­[2.2.1]heptane-5,6-diol]

Simone, M.; Fleet, G.W.J.; Watkin, D.J.

doi:10.1107/S160053680700311X

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 63| Part 2| February 2007| Pages o896-o897

https://doi.org/10.1107/S160053680700311X

1,5-Anhydro-2,3-O-isopropylidene-L-lyxofuranose [(1S,4S,5S,6R)-5,6-O-isopropylidene-2,7-dioxabicyclo[2.2.1]heptane-5,6-diol]

Michela Simone,^a ^* George W. J. Fleet ^a and David J. Watkin ^b

^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: michela_simone@yahoo.co.uk

(Received 14 December 2006; accepted 19 January 2007; online 24 January 2007)

The tricyclic title compound, C₈H₁₂O₄, was formed in the reduction by diisobutylaluminium hydride of a 5-O-trifluromethanesulfonyl lactone and is likely to be useful as a chiral intermediate for the synthesis of bioactive compounds. The absolute configuration was determined by the use of 2,3-O-isopropylidene-L-lyxono-1,4-lactone as the starting material.

Comment

Branched sugar lactones may be useful as versatile intermediates in the synthesis of novel branched biologically important molecules and biopolymeric materials (Asano et al., 2000 ; Ichikawa & Igarashi, 1995 ; Ichikawa et al., 1998 ; Soengas et al., 2005 ; Hotchkiss et al., 2004 , 2006 ). The Ho crossed-aldol reaction (Ho, 1979 , 1985 ) of lactols with formaldehyde is one of the most powerful strategies for the synthesis of these compounds. In the course of the synthesis of a branched sugar lactone by a Ho procedure (Simone et al., 2005 ), the trifluoromethanesulfonate, (2), derived from the 2,3-O-isopropylidene-L-lyxono-1,4-lactone, (1) (Simone et al., 2005), was treated with diisobutylaluminium hydride (DIBAL-H). A rationalization for the formation of the title compound, (4), is that initial reduction afforded the β-lyxose, (3), which spontaneously cyclized to (4) by S_N2 displacement of the trifluoromethanesulfonate. The value of such highly oxygenated bicyclic intermediates as (4) is well established (Cossy et al., 1995 ; Pechy et al., 1993 ), and the unexpected formation of (4) may provide another valuable chiron.

The structure of (4) has been determined by X-ray diffraction (Fig. 1), which showed that it is formed by a six-membered ring fused to a five-membered ring (the acetonide protecting group). The five-membered ring adopts an envelope conformation. The six-membered ring is a B_2,5-type conformationally constrained structure, due to the existence of the oxygen bridge linking the 1- and 4-positions.

Figure 1
The molecular structure of the title compound, with displacement ellipsoids drawn at the 50% probability level. H atoms are shown as spheres of arbitary radius.

Experimental

1,5-Anhydro-2,3-O-isopropylidene-L-lyxofuranose, (4), was obtained in 28% yield upon overnight reduction of the trifluoromethanesulfonate (2) with DIBAL-H in tetrahydrofuran at low concentration (16 mg ml⁻¹). The title material, (4), isolated as a crystalline but volatile product, was recrystallized via solvent evaporation (ethyl acetate–cyclohexane) (R_f 0.57; m.p. 338–339 K). HRMS (FI⁺), found: 172.0732 [M]⁺; C₈H₁₂O₄ requires: 172.0736; [α]_D²¹ 106.8 (c, 0.72 in methanol); IR (thin film, ν_max, cm⁻¹): 2992, 2955, 2906 (s, C—H), 1378 (–O—CO—CH), 1291 (C—O); ¹H NMR (CDCl₃, 400 MHz): δ 1.34, 1.60 [2 × 3H, 2 × s, C(CH₃)₂], 3.55 (1H, ddd, J_H5,H5′ = 6.6 Hz, J_H5,H4 = 3.5 Hz, J_H5,H3 = 1.3 Hz, H5), 4.31 (1H, a–d, J = 6.8 Hz, H5′), 4.45 (1H, a–dd, J = 8.2 and 2.3 Hz, H2), 4.64 (1H, dd, J_H3,H2 = 8.1 Hz, J_H3,H4 = 4.6 Hz, H3), 4.72–4.77 (1H, m, H4), 5.45 (1H, d, J_H1,H2 = 2.2 Hz, H1); ¹³C NMR (CDCl₃, 100 MHz): δ 25.6, 26.1 [C(CH₃)₂], 63.7 (C5), 76.5 (C3), 78.8 (C4), 81.6 (C2), 100.1 (C1), 119.7 [C(CH₃)₂].

Crystal data

C₈H₁₂O₄
M_r = 172.18
Orthorhombic, P 2₁ 2₁ 2₁
a = 8.1279 (3) Å
b = 9.4993 (4) Å
c = 10.8126 (4) Å
V = 834.83 (6) Å³
Z = 4
D_x = 1.370 Mg m⁻³
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 150 K
Fragment, colourless
0.38 × 0.32 × 0.14 mm

Data collection

Nonius KappaCCD area-detector diffractometer
ω scans
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.96, T_max = 0.98
5825 measured reflections
1111 independent reflections
834 reflections with I > 3σ(I)
R_int = 0.037
θ_max = 27.4°

Refinement

Refinement on F
R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.031
S = 1.15
834 reflections
109 parameters
H-atom parameters constrained
w = [1 − (F_o − F_c)²/36σ²(F)]²/[0.275T₀(x) + 0.0396T₁(x) + 0.0219T₂(x)] where T_i are Chebychev polynomials and x = F_c/F_max (Prince, 1982 ; Watkin, 1994 )
(Δ/σ)_max = 0.005
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.14 e Å⁻³

A large single-crystal was cut to give a small fragment. This was mounted on a glass fibre using perfluoropolyether oil and cooled rapidly to 150 K in a stream of cold N₂ using an Oxford Cryosystems CRYOSTREAM unit. H atoms were positioned geometrically after each cycle of refinement, with C—H = 1.00 Å and U_iso(H) = 1.2U_eq(C).

Data collection: COLLECT (Nonius, 2000 ); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: DENZOand 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.

Supporting information

Crystal structure: contains datablocks global, 4. DOI: https://doi.org/10.1107/S160053680700311X/fl2085sup1.cif

Structure factors: contains datablock 4. DOI: https://doi.org/10.1107/S160053680700311X/fl20854sup2.hkl

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: DENZO (Otwinowski & Minor, 1997); data reduction: 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: CAMERON (Watkin et al., 1996); software used to prepare material for publication: CRYSTALS.

(1S,4S,5S,6R)-5,6-O-isopropylidene-2,7-dioxabicyclo[2.2.1]heptane-5,6-diol top

Crystal data top

C₈H₁₂O₄	D_x = 1.370 Mg m⁻³
M_r = 172.18	Mo Kα radiation, λ = 0.71073 Å
Orthorhombic, P2₁2₁2₁	Cell parameters from 5825 reflections
a = 8.1279 (3) Å	θ = 5–28°
b = 9.4993 (4) Å	µ = 0.11 mm⁻¹
c = 10.8126 (4) Å	T = 150 K
V = 834.83 (6) Å³	Fragment, colourless
Z = 4	0.38 × 0.32 × 0.14 mm
F(000) = 368

Data collection top

Nonius KappaCCD area-detector diffractometer	834 reflections with I > 3σ(I)
Graphite monochromator	R_int = 0.037
ω scans	θ_max = 27.4°, θ_min = 5.3°
Absorption correction: multi-scan (DENZO and SCALEPACK; Otwinowski & Minor, 1997)	h = −10→10
T_min = 0.96, T_max = 0.98	k = −12→12
5825 measured reflections	l = −14→14
1111 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)] = 0.031	H-atom parameters constrained
wR(F²) = 0.031	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 A_i are: 0.275 0.396E-01 0.219E-01. Part 2 robust weighting (Prince, 1982) W = [weight][1-(δF/6*σF)²]²
S = 1.15	(Δ/σ)_max = 0.005
834 reflections	Δρ_max = 0.14 e Å⁻³
109 parameters	Δρ_min = −0.14 e Å⁻³
0 restraints

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

	x	y	z	U_iso*/U_eq
C1	0.1736 (3)	0.6521 (2)	0.62753 (19)	0.0262
C2	0.3607 (2)	0.6634 (2)	0.64715 (18)	0.0235
C3	0.3853 (3)	0.5599 (2)	0.75558 (18)	0.0264
C4	0.2093 (3)	0.5067 (2)	0.77520 (19)	0.0298
C5	0.1561 (3)	0.4181 (2)	0.6659 (2)	0.0358
O1	0.13420 (19)	0.52285 (17)	0.56943 (13)	0.0325
O2	0.45774 (16)	0.60634 (15)	0.54954 (12)	0.0246
O3	0.49639 (19)	0.45713 (16)	0.71003 (12)	0.0306
O4	0.11892 (18)	0.63636 (16)	0.75191 (13)	0.0316
C6	0.5795 (2)	0.5186 (2)	0.60626 (18)	0.0268
C7	0.6269 (3)	0.4035 (3)	0.5179 (2)	0.0431
C8	0.7237 (3)	0.6058 (3)	0.6504 (2)	0.0447
H11	0.1273	0.7317	0.5781	0.0314*
H21	0.3938	0.7642	0.6568	0.0282*
H31	0.4319	0.5955	0.8352	0.0317*
H41	0.1953	0.4551	0.8551	0.0358*
H51	0.0508	0.3676	0.6837	0.0429*
H52	0.2429	0.3483	0.6429	0.0429*
H71	0.7120	0.3419	0.5571	0.0517*
H72	0.6727	0.4460	0.4406	0.0517*
H73	0.5276	0.3460	0.4972	0.0517*
H81	0.8073	0.5429	0.6897	0.0536*
H82	0.6846	0.6765	0.7123	0.0536*
H83	0.7744	0.6557	0.5785	0.0536*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0237 (10)	0.0306 (11)	0.0243 (10)	0.0031 (9)	0.0010 (8)	0.0031 (10)
C2	0.0241 (10)	0.0220 (9)	0.0243 (10)	0.0003 (9)	−0.0012 (8)	−0.0025 (8)
C3	0.0275 (10)	0.0338 (11)	0.0178 (9)	0.0083 (9)	−0.0009 (9)	−0.0026 (9)
C4	0.0298 (11)	0.0348 (12)	0.0248 (10)	0.0072 (10)	0.0047 (8)	0.0073 (10)
C5	0.0346 (12)	0.0297 (12)	0.0430 (13)	−0.0075 (10)	0.0055 (11)	0.0029 (10)
O1	0.0265 (8)	0.0433 (9)	0.0277 (8)	−0.0068 (8)	−0.0028 (6)	−0.0017 (7)
O2	0.0215 (7)	0.0308 (7)	0.0215 (7)	0.0012 (6)	−0.0001 (6)	0.0031 (6)
O3	0.0313 (7)	0.0344 (8)	0.0259 (7)	0.0118 (7)	0.0052 (6)	0.0080 (7)
O4	0.0293 (7)	0.0390 (9)	0.0265 (7)	0.0094 (7)	0.0047 (7)	0.0008 (7)
C6	0.0225 (10)	0.0370 (12)	0.0209 (9)	0.0048 (9)	0.0004 (7)	0.0060 (10)
C7	0.0461 (14)	0.0475 (14)	0.0358 (13)	0.0176 (13)	0.0073 (12)	−0.0046 (12)
C8	0.0236 (11)	0.0646 (18)	0.0457 (14)	−0.0058 (12)	−0.0070 (10)	0.0042 (15)

Geometric parameters (Å, º) top

C1—C2	1.539 (3)	C5—O1	1.453 (3)
C1—O1	1.416 (3)	C5—H51	1.000
C1—O4	1.424 (2)	C5—H52	1.000
C1—H11	1.000	O2—C6	1.432 (2)
C2—C3	1.543 (3)	O3—C6	1.434 (2)
C2—O2	1.425 (2)	C6—C7	1.503 (3)
C2—H21	1.000	C6—C8	1.512 (3)
C3—C4	1.532 (3)	C7—H71	1.000
C3—O3	1.418 (2)	C7—H72	1.000
C3—H31	1.000	C7—H73	1.000
C4—C5	1.514 (3)	C8—H81	1.000
C4—O4	1.456 (3)	C8—H82	1.000
C4—H41	1.000	C8—H83	1.000

C2—C1—O1	110.19 (17)	O1—C5—H51	111.212
C2—C1—O4	100.70 (16)	C4—C5—H52	111.212
O1—C1—O4	104.89 (17)	O1—C5—H52	111.211
C2—C1—H11	113.145	H51—C5—H52	109.466
O1—C1—H11	109.473	C1—O1—C5	104.34 (15)
O4—C1—H11	117.841	C2—O2—C6	106.66 (14)
C1—C2—C3	100.84 (17)	C3—O3—C6	106.94 (15)
C1—C2—O2	114.72 (17)	C1—O4—C4	95.43 (15)
C3—C2—O2	104.40 (15)	O2—C6—O3	104.26 (15)
C1—C2—H21	110.280	O2—C6—C7	109.17 (17)
C3—C2—H21	119.725	O3—C6—C7	108.77 (18)
O2—C2—H21	107.052	O2—C6—C8	110.63 (18)
C2—C3—C4	101.21 (16)	O3—C6—C8	109.94 (17)
C2—C3—O3	104.90 (15)	C7—C6—C8	113.64 (19)
C4—C3—O3	114.58 (17)	C6—C7—H71	109.467
C2—C3—H31	119.186	C6—C7—H72	109.467
C4—C3—H31	110.269	H71—C7—H72	109.476
O3—C3—H31	106.897	C6—C7—H73	109.467
C3—C4—C5	109.99 (17)	H71—C7—H73	109.476
C3—C4—O4	99.71 (16)	H72—C7—H73	109.476
C5—C4—O4	101.03 (16)	C6—C8—H81	109.467
C3—C4—H41	112.794	C6—C8—H82	109.467
C5—C4—H41	111.682	H81—C8—H82	109.476
O4—C4—H41	120.440	C6—C8—H83	109.467
C4—C5—O1	102.39 (16)	H81—C8—H83	109.475
C4—C5—H51	111.212	H82—C8—H83	109.475

Acknowledgements

Financial support to MS provided through the European Community's Human Potential Programme under contract No. HPRN-CT-2002–00173 is gratefully acknowledged.

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