(1R,2S,5R)-(–)-Menthyl (S)-2-(methoxy­carbonyl)­benzene­sulfinate

Maria Altamura; Antonio Guidi; Loic Jierry; Paola Paoli; Patrizia Rossi

doi:10.1107/S1600536813009112

. 2013 Apr 13;69(Pt 5):o731. doi: 10.1107/S1600536813009112

(1R,2S,5R)-(–)-Menthyl (S)-2-(methoxycarbonyl)benzenesulfinate

Maria Altamura ^a, Antonio Guidi ^a, Loic Jierry ^b, Paola Paoli ^c,^*, Patrizia Rossi ^c

PMCID: PMC3648263 PMID: 23723883

Abstract

In the title chiral sulfinic acid ester, C₁₈H₂₆O₄S, the cyclohexane ring of the menthyl fragment adopts a chair conformation. The molecular shape is defined by the dihedral angle of 47.87 (8)° between the mean planes of the cyclohexane and benzene rings. In the crystal, molecules related by the screw axis are connected into chains along [010] by weak C_ar—H⋯O=S contacts.

Related literature

For the synthesis of the title compound, see: Klunder & Sharpless (1987 ▶) and of chiral sulfoxides, see: Drabowicz et al. (1982 ▶); Solladié et al. (1987 ▶). For applications of menthol in synthetic chemistry, see Oertling et al. (2007 ▶). For structural studies of analogous chiral sulfinic acid esters, see: Mariz et al. (2010 ▶); Heinemann et al. (2007 ▶); Cherkaoui & Nicoud (1995 ▶). graphic file with name e-69-0o731-scheme1.jpg

Experimental

Crystal data

C₁₈H₂₆O₄S
M _r = 338.45
Monoclinic,
a = 9.7918 (2) Å
b = 9.3938 (2) Å
c = 10.6998 (2) Å
β = 112.176 (2)°
V = 911.39 (3) Å³
Z = 2
Cu Kα radiation
μ = 1.72 mm⁻¹
T = 150 K
0.26 × 0.22 × 0.08 mm

Data collection

Oxford Diffraction Xcalibur PX diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2006 ▶) T _min = 0.660, T _max = 0.872
4681 measured reflections
2354 independent reflections
2115 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.078
S = 1.07
2354 reflections
209 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.22 e Å⁻³
Absolute structure: Flack (1983 ▶), 767 Friedel pairs
Flack parameter: 0.038 (18)

Data collection: CrysAlis CCD (Oxford Diffraction, 2006 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2006 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: PARST (Nardelli, 1995 ▶).

Supplementary Material

Click here for additional data file.^{(18.7KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813009112/yk2089sup1.cif

e-69-0o731-sup1.cif^{(18.7KB, cif)}

Click here for additional data file.^{(113.3KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813009112/yk2089Isup2.hkl

e-69-0o731-Isup2.hkl^{(113.3KB, hkl)}

Click here for additional data file.^{(6.5KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813009112/yk2089Isup3.cml

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
C5—H5⋯O4ⁱ	0.95	2.42	3.337 (3)	161

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge the CRIST (Centro di Cristallografia Strutturale, University of Firenze), where the data collection was performed.

supplementary crystallographic information

Comment

As a result of the trigonal pyramidal stereochemistry which characterizes the sulfur atom in organic sulfinic acid esters and sulfoxides bearing two different substituents, these species are chiral. Chiral sulfoxides are key intermediates for asymmetric synthesis and can be obtained from the reaction of an organometallic reagent (e.g. a Grignard reagent) with a diastereomerically pure sulfinate ester of menthol (Drabowicz et al., 1982). On the other hand, menthyl sulfinates can be prepared by reaction of menthol (Oertling et al., 2007) either with sodium sulfinates (Solladié et al., 1987) or with a sulfonyl chloride in the presence of trimethylphosphite as in situ reducing agent (Klunder & Sharpless, 1987). We used the latter method to prepare the chiral sulfinic acid ester, (1R,2S,5R)-(-)-menthyl (S)-2-carbomethoxybenzenesulfinate, here reported. The overall molecular shape of the title compound depends on the dihedral angle formed between the mean plane defined by the ring atoms of the menthyl and of the phenyl groupings (132.13°(8)). Bond distances and angles about the sulfur atom, as well as the orientation of the isopropyl chain with respect to the menthyl ring are in keeping with those already reported for this molecular fragment (Heinemann et al., 2007; Mariz et al., 2010; Cherkaoui & Nicoud, 1995). In the crystal, molecules are connected via weak C_ar—H···O contacts involving the double bonded oxygen atom of the sulfinate group as acceptor. The resulting molecular chain propagates along the b axis direction around the screw axis.

Experimental

For the synthesis of the title compound, see: Klunder & Sharpless (1987). Crystals of the title compound suitable for single-crystal X-ray diffraction analysis were obtained by slow evaporation from a diethyl ether solution of the sulfinate ester.