(3R,4S)-3,4-Isopropyl­idenedioxy-3,4-dihydro-2H-pyrrole 1-oxide

Mari Fe Flores; Pilar Garcia; Narciso M Garrido; Francisca Sanz; David Diez

doi:10.1107/S1600536811013055

. 2011 Apr 13;67(Pt 5):o1116–o1117. doi: 10.1107/S1600536811013055

(3R,4S)-3,4-Isopropylidenedioxy-3,4-dihydro-2H-pyrrole 1-oxide

Mari Fe Flores ^a, Pilar Garcia ^a, Narciso M Garrido ^a, Francisca Sanz ^b, David Diez ^a,^*

PMCID: PMC3089370 PMID: 21754432

Abstract

The title compound C₇H₁₁NO₃ was prepared by intramolecular nucleophilic displacement of 2,3-O-iso-propylidene-d-erythronolactol. There are two molecules in the asymmetric unit, which are related by a pseudo-inversion centre. The crystal structure determination confirms unequivocally the configuration of the chiral centres as 3S,4R. In the crystal structure, intermolecular C—H⋯O interactions link the molecules (into infinite zigzag chains along the a axis.

Related literature

Nitrones play a useful role in the synthesis of complex molecular frameworks, undergoing several synthetically useful reactions such as 1,3-dipolar cycloadditions (Tufariello, 1984 ▶) and nucleophilic addition (Merino et al., 2000 ▶; Lombardo & Trombini, 2002 ▶). They also allow direct access to nitrones by simple reactions, see: Döpp & Döpp (1990 ▶); Hamer & Macaluso (1964 ▶). For the use of the title compound as a starting material in the sythesis of potential therapeutic (antibiotic, antiviral, antitumoral) agents, see: Hall et al. (1997 ▶); Closa & Wightman (1998 ▶); McCaig et al. (1998 ▶); Cicchi et al. (2002 ▶); Revuelta et al. (2007 ▶). For a related structure, see: Keleşoğlu et al. (2010 ▶). For the preparation of the title compound, see: Flores et al. (2010 ▶); Cicchi et al. (2006 ▶). graphic file with name e-67-o1116-scheme1.jpg

Experimental

Crystal data

C₇H₁₁NO₃
M _r = 157.17
Monoclinic,
a = 11.335 (2) Å
b = 5.4467 (11) Å
c = 26.508 (5) Å
β = 101.40 (3)°
V = 1604.2 (6) Å³
Z = 8
Cu Kα radiation
μ = 0.86 mm⁻¹
T = 298 K
0.15 × 0.10 × 0.08 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T _min = 0.902, T _max = 0.934
4369 measured reflections
2365 independent reflections
2261 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.091
S = 1.05
2365 reflections
204 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.11 e Å⁻³
Absolute structure: Flack (1983 ▶), 761 Friedel pairs
Flack parameter: 0.0 (2)

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811013055/bt5507sup1.cif

e-67-o1116-sup1.cif^{(18.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013055/bt5507Isup2.hkl

e-67-o1116-Isup2.hkl^{(116.2KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O1ⁱ	0.93	2.44	3.366 (3)	171
C1—H1⋯O3ⁱⁱ	0.98	2.38	3.355 (3)	171
C2—H2A⋯O3ⁱⁱⁱ	0.97	2.70	3.441 (3)	134
C2—H2B⋯O3^iv	0.97	2.41	3.120 (3)	130
C2′—H2′1⋯O2′^v	0.97	2.49	3.247 (2)	135
C4′—H4′⋯O3′^vi	0.98	2.48	3.375 (3)	152
C2′—H2′2⋯O3′^vii	0.97	2.61	3.254 (2)	124
C3′—H3′⋯O3′^viii	0.93	2.48	3.345 (3)	156

Open in a new tab

Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .

Acknowledgments

The authors are grateful to the MICINN (CTQ2009–11172), Junta de Castilla y Leon, for financial support (GR178 and SA001A09) and for the doctoral fellowships awarded to MFF.

supplementary crystallographic information

Comment

Nitrones have been the subject of intense research efforts, because of the wide role played in the synthesis of complex molecular frameworks. They undergo several synthetically useful reactions such as 1,3-dipolar cycloadditions, (Tufariello et al., 1984) nucleophilic additions, (Merino et al., 2000; Lombardo et al., 2002). Both the reactions give rise to the formation of new carbon-carbon bonds, often with a high degree of stereocontrol. These features, together with the direct access to nitrones by simple reactions (Hamer et al., 1964; Döpp et al., 1990), and their stability which permits isolation and long storage, make nitrones ideal tools for application in organic syntheses, particularly in the field of alkaloids, nitrogen containing natural products or bioactive analogues. The construction of highly functionalized nitrogen heterocycles in a stereoselective manner is an important focus of medicinal and natural product chemistry. Although, in the last few years, the title compound has been reported more and more in the literature as a starting material due to its biological relevance in the synthesis of polyhydroxypyrrolidines or polyhydroxypyrrolizidines, both interesting compounds as potential glycosidase inhibitors and consequently as potential therapeutic (antibiotic, antiviral, antitumoral) agents (Hall et al., 1997; Closa et al., 1998; McCaig et al., 1998; Cicchi et al., 2002; Revuelta et al., 2007) there was not any crystallographic data.

Following our special interest in nitrogen compounds such as isoxazolidines, we prepared the title N-oxide, and its crystal structure is reported here.

The asymmetric unit contains two symmetrically independent molecules. The title molecule consists of a pyrroline-N-oxide ring with an isopropylidenedioxy as substituent. All the bond lengths and angles are within the normal ranges. The carbonyl group at N1 is coplanar with the pyrroline ring being the O3—N1=C3—C4 and O3'-N1'=C3'-C4' torsion angles of 179.1 (4)° and 179.2 (7)°, respectively. These results are in good agreement with the literature (Keleşoğlu et al., 2010).

In the crystal structure, intermolecular C—H···O interactions (Table 1) link the molecules (Fig. 2) into infinite zigzag chains along the a axis.

Experimental

The title N-oxide was obtained by intramolecular nucleophilic displacement, which is based on a simple one-pot procedure employing NH₂OSiMe₂t-Bu, methanesulfonyl chloride, and 2,3-O-iso-propylidene-D-erythronolactol, according to the methodology described by Cicchi et al. (2006) and by us (Flores et al., 2010). Well shaped colourless single crystals were obtained by crystallization from CH₂Cl₂/MeOH.