1-[(4S)-4-Benzyl-2-thioxo-1,3-thia­zol­idin-3-yl]propan-1-one

Narendar Reddy Gade; Y Manjula; Javed Iqbal; Peddy Vishweshwar

doi:10.1107/S1600536809030104

. 2009 Aug 15;65(Pt 9):o2159. doi: 10.1107/S1600536809030104

1-[(4S)-4-Benzyl-2-thioxo-1,3-thiazolidin-3-yl]propan-1-one¹

Narendar Reddy Gade ^a, Y Manjula ^b, Javed Iqbal ^a,^*, Peddy Vishweshwar ^b,^*

PMCID: PMC2970139 PMID: 21577567

Abstract

The analysis of the title chiral auxiliary compound, C₁₃H₁₅NOS₂, has enabled the determination of the absolute configuration at the benzyl-bearing ring C atom as S. In the crystal structure, molecules aggregate into helical chains along the b axis via C—H⋯O contacts.

Related literature

For background to the use of N-acyl thiazolidinethiones as versatile chiral auxiliaries for asymmetric aldol reactions, see: Crimmins & Chaudhary (2000 ▶); Crimmins et al. (2005 ▶); Crimmins & Haley (2006 ▶); Crimmins & Dechert (2009 ▶). For the synthesis, see: McKennon & Meyer (1993 ▶); Delaunay et al. (1995 ▶); Lu et al. (2009 ▶).

Experimental

Crystal data

C₁₃H₁₅NOS₂
M _r = 265.39
Monoclinic,
a = 8.850 (6) Å
b = 7.189 (5) Å
c = 10.595 (7) Å
β = 95.537 (6)°
V = 670.9 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.38 mm⁻¹
T = 298 K
0.50 × 0.40 × 0.20 mm

Data collection

Rigaku Mercury diffractometer
Absorption correction: multi-scan (Jacobson, 1998 ▶) T _min = 0.831, T _max = 0.925
7301 measured reflections
2734 independent reflections
2361 reflections with F ² > 2σ(F ²)
R _int = 0.038

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.048
S = 0.86
2734 reflections
170 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.35 e Å⁻³
Absolute structure: Flack (1983 ▶), 1138 Friedel pairs
Flack parameter: −0.05 (6)

Data collection: CrystalClear (Pflugrath, 1999 ▶); cell refinement: CrystalClear; data reduction: CrystalStructure (Molecular Structure Corporation & Rigaku, 2006 ▶); program(s) used to solve structure: SIR2004 (Burla et al., 2005 ▶); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003 ▶); molecular graphics: X-SEED (Barbour et al., 2001 ▶); software used to prepare material for publication: CrystalStructure.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809030104/tk2514sup1.cif

e-65-o2159-sup1.cif^{(16.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809030104/tk2514Isup2.hkl

e-65-o2159-Isup2.hkl^{(149.7KB, 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
C9—H9⋯O1ⁱ	0.95	2.55	3.408 (4)	150

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Symmetry code: (i) Inline graphic .

Acknowledgments

NRG thanks the Institute of Life Sciences for allowing him to pursue this work as part of his PhD thesis.

supplementary crystallographic information

Comment

N-Acyl thiazolidinethiones, e.g. (I), are versatile chiral auxiliaries for asymmetric aldol reactions Crimmins & Chaudhary (2000). Many complex natural products have been synthesized using these auxiliaries (Crimmins et al. 2005; Crimmins & Haley, 2006; Crimmins & Dechert, 2009). The synthesis of (I) starts from amino alcohol 2 which was converted to thiazolidinethione 3 by reacting with carbon disulfide followed by treatment with propionyl chloride (Fig. 3) (Crimmins & Chaudhary, 2000).

The single crystal analysis of (I), Fig. 1, allowed the determination of the absolute configuration of C1 as S. The crystal structure shows the molecules to aggregate into helical chains along the screw axis via C₉—H₉···O₁ contacts (Fig. 2, Table 1).

Experimental

To a solution of β-amino alcohol 2 (10 mmol) (McKennon & Meyer, 1993) in aqueous 1.0 N potassium hydroxide (50 ml) was added carbon disulfide (50 mmol, 3.0 ml) slowly. The reaction mixture was refluxed at 110 °C for 12 h to give the desired thiazolidinethione 3 (Delaunay et al. 1995). To a solution of compound 3 (0.478 mmol) in dichloromethane (DCM, 3 ml) was added triethylamine (0.956 mmol) and the temperature was maintained at -40 to -78 °C. To that mixture was added propionyl chloride (0.574 mmol) drop wise. The mixture was stirred for 1–2 h, diluted with DCM (10 ml), washed with water (2 x 10 ml), dried over anhydrous Na₂SO₄ and concentrated low vacuum to give (I) as a light-yellow solid; mp. 374–376 K (lit. mp. 374.1 K (Lu et al. 2009)).

Compound (I) (50 mg) was dissolved in 2:1 DCM/EtOAC (1.0 ml) and left in freezer (10 °C) until fine crystals appeared. Crystals were separated from soluton and washed with hexane and dried under vacuum.