Crystal structure of methyl (2R,3S)-3-[(tert-butyl­sulfin­yl)amino]-2-fluoro-3-phenyl­propano­ate

Zhiwei Zhao; Wenqiang Fan; Yixiang Zhang; Ya Li

doi:10.1107/S2056989015023580

. 2015 Dec 16;71(Pt 12):o1055–o1056. doi: 10.1107/S2056989015023580

Crystal structure of methyl (2R,3S)-3-[(tert-butylsulfinyl)amino]-2-fluoro-3-phenylpropanoate

Zhiwei Zhao ^a, Wenqiang Fan ^a, Yixiang Zhang ^a, Ya Li ^a,^*

PMCID: PMC4719976 PMID: 26870495

Abstract

The title compound, C₁₄H₂₀FNO₃S, contains two chiral carbon centres and the absolute configuration has been confirmed as (2R,3S). In the crystal, adjacent molecules are linked by weak C—H⋯O hydrogen bonds, generating zigzag chains along the a-axis direction.

Keywords: crystal structure, fluorine, amino acid, sulfoxide, N—H⋯O hydrogen bonding

Related literature

For the use of of fluorinated β-amino acids in organic synthesis, see: Marsh (2014 ▸); Niemz & Tirrell (2001 ▸); Chiu et al. (2006 ▸). For their synthesis, see: Shang et al. (2015 ▸); Yoshinari et al. (2011 ▸); Duggan et al. (2010 ▸); Peddie & Abell (2012 ▸); Jing et al. (2011 ▸); Pan et al. (2010 ▸). graphic file with name e-71-o1055-scheme1.jpg

Experimental

Crystal data

C₁₄H₂₀FNO₃S
M _r = 301.37
Orthorhombic,
a = 9.1809 (14) Å
b = 9.2384 (15) Å
c = 18.577 (3) Å
V = 1575.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 296 K
0.13 × 0.11 × 0.07 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▸) T _min = 0.972, T _max = 0.985
8176 measured reflections
2773 independent reflections
2542 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.033
wR(F ²) = 0.088
S = 1.04
2773 reflections
186 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.29 e Å⁻³
Absolute structure: Flack (1983 ▸)
Absolute structure parameter: 0.05 (8)

Data collection: APEX2 (Bruker, 2007 ▸); cell refinement: SAINT (Bruker, 2007 ▸); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▸); molecular graphics: SHELXTL (Sheldrick, 2008 ▸) and PLATON (Spek, 2009 ▸); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015023580/su5256sup1.cif

e-71-o1055-sup1.cif^{(17.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015023580/su5256Isup2.hkl

e-71-o1055-Isup2.hkl^{(136.2KB, hkl)}

Click here for additional data file.^{(5.5KB, cml)}

Supporting information file. DOI: 10.1107/S2056989015023580/su5256Isup3.cml

Click here for additional data file.^{(1.5MB, tif)}

. DOI: 10.1107/S2056989015023580/su5256fig1.tif

Molecular structure of the title compound, with atom labeling. Displacement ellipsoids are drawn at the 50% probability level.

Click here for additional data file.^{(1,013.4KB, tif)}

c . DOI: 10.1107/S2056989015023580/su5256fig2.tif

A partial view along the c axis of the crystal packing of the title compound. Hydrogen bonds are shown as dashed lines (see Table 1).

CCDC reference: 1441329

Additional supporting information: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C14—H14B⋯O3ⁱ	0.96	2.79	3.045 (4)	135

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Symmetry code: (i) Inline graphic .

Acknowledgments

Financial support by the Innovation Program of Shanghai University Students (cs1504006) is gratefully acknowledged.

supplementary crystallographic information

S1. Synthesis and crystallization

LiHMDS (1.5 ml, 1.0 mol/l in THF) was added to a solution of methyl fluoroacetate (138 mg, 1.5 mmol), (Rs)—N-benzylidene- 2-methylpropane-2-sulfinamide (209 mg, 1.0 mmol), N,N,N',N'-tetramethyl-ethane-1,2-diamine (0.3 ml), and THF (3 ml) at 203 K. The reaction mixture was stirred for 30 min, then saturated NH₄Cl—H₂O (5 ml) was added, and the quenched reaction mixture was extracted with ethyl acetate (3 × 20 ml). The combined organic layers were dried over anhydrous Na₂SO₄. The obtained compound was recrystallized from ethyl acetate/hexane (1:2) to give colorless crystals.

S1.1. Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2. A l l the H atoms were placed at calculated positions and treated as riding atoms: N—H = 0.86 Å, C—H = 0.93–0.96 Å with U_iso(H) = 1.5U_eq(C-methyl and 1.2U_eq(N,C) for other H atoms.