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

Zhao, Z.; Fan, W.; Zhang, Y.; Li, Y.

doi:10.1107/S2056989015023580

organic compounds

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Volume 71| Part 12| December 2015| Pages o1055-o1056

https://doi.org/10.1107/S2056989015023580

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

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

^aDepartment of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, 333 Longteng Road, Shanghai, People's Republic of China
^*Correspondence e-mail: ya.li@sues.edu.cn

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 3 December 2015; accepted 9 December 2015; online 16 December 2015)

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.

CCDC reference: 1441329

1. 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 ).

2. Experimental

2.1. Crystal data

C₁₄H₂₀FNO₃S
M_r = 301.37
Orthorhombic, P 2₁ 2₁ 2₁
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

2.2. 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

2.3. Refinement

R[F² > 2σ(F²)] = 0.033
wR(F²) = 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)

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
Symmetry code: (i) x-1, y, z.

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.

Supporting information

CCDC reference: 1441329

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: https://doi.org/10.1107/S2056989015023580/su5256sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2056989015023580/su5256Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2056989015023580/su5256Isup3.cml

checkCIF report

Synthesis and crystallization top

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.

Refinement top

Crystal data, data collection and structure refinement details are summarized in Table 2. All 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.

Related literature top

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).

Structure description top

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).

Synthesis and crystallization top

Refinement details top

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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 (Sheldrick, 2008).

Figures top

	Fig. 1. Molecular structure of the title compound, with atom labeling. Displacement ellipsoids are drawn at the 50% probability level.
	Fig. 2. 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).

Methyl (2R,3S)-3-[(tert-butylsulfinyl)amino]-2-fluoro-3-phenylpropanoate top

Crystal data top

C₁₄H₂₀FNO₃S	F(000) = 640
M_r = 301.37	D_x = 1.270 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3418 reflections
a = 9.1809 (14) Å	θ = 2.2–25.5°
b = 9.2384 (15) Å	µ = 0.22 mm⁻¹
c = 18.577 (3) Å	T = 296 K
V = 1575.7 (4) Å³	Block, colorless
Z = 4	0.13 × 0.11 × 0.07 mm

Data collection top

Bruker APEXII CCD diffractometer	2773 independent reflections
Radiation source: fine-focus sealed tube	2542 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.022
φ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2007)	h = −7→10
T_min = 0.972, T_max = 0.985	k = −11→11
8176 measured reflections	l = −22→21

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.033	w = 1/[σ²(F_o²) + (0.0505P)² + 0.1714P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.088	(Δ/σ)_max < 0.001
S = 1.04	Δρ_max = 0.27 e Å⁻³
2773 reflections	Δρ_min = −0.29 e Å⁻³
186 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
0 restraints	Extinction coefficient: 0.0117 (16)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), ???? Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.05 (8)

Crystal data top

C₁₄H₂₀FNO₃S	V = 1575.7 (4) Å³
M_r = 301.37	Z = 4
Orthorhombic, P2₁2₁2₁	Mo Kα radiation
a = 9.1809 (14) Å	µ = 0.22 mm⁻¹
b = 9.2384 (15) Å	T = 296 K
c = 18.577 (3) Å	0.13 × 0.11 × 0.07 mm

Data collection top

Bruker APEXII CCD diffractometer	2773 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2007)	2542 reflections with I > 2σ(I)
T_min = 0.972, T_max = 0.985	R_int = 0.022
8176 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.033	H-atom parameters constrained
wR(F²) = 0.088	Δρ_max = 0.27 e Å⁻³
S = 1.04	Δρ_min = −0.29 e Å⁻³
2773 reflections	Absolute structure: Flack (1983), ???? Friedel pairs
186 parameters	Absolute structure parameter: 0.05 (8)
0 restraints

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
S1	0.45246 (5)	0.13512 (6)	1.04644 (3)	0.04566 (16)
C1	0.4525 (2)	0.0513 (2)	0.86771 (10)	0.0454 (5)
C2	0.4258 (3)	0.1407 (3)	0.80959 (13)	0.0645 (7)
H2	0.3412	0.1960	0.8085	0.077*
C3	0.5233 (3)	0.1489 (4)	0.75313 (14)	0.0799 (8)
H3	0.5032	0.2089	0.7142	0.096*
C4	0.6486 (3)	0.0701 (4)	0.75394 (14)	0.0790 (9)
H4	0.7134	0.0755	0.7156	0.095*
C5	0.6780 (3)	−0.0166 (3)	0.81134 (15)	0.0763 (8)
H5	0.7640	−0.0698	0.8124	0.092*
C6	0.5812 (3)	−0.0262 (3)	0.86807 (13)	0.0614 (6)
H6	0.6029	−0.0855	0.9070	0.074*
C7	0.3370 (2)	0.0338 (2)	0.92539 (10)	0.0412 (4)
H7	0.2837	0.1254	0.9288	0.049*
C8	0.2285 (2)	−0.0833 (2)	0.90203 (11)	0.0485 (5)
H8	0.1834	−0.0536	0.8566	0.058*
C9	0.1100 (2)	−0.1116 (2)	0.95639 (13)	0.0467 (5)
C10	0.3929 (3)	0.0729 (3)	1.13521 (12)	0.0606 (6)
C11	0.4604 (4)	0.1814 (4)	1.18744 (15)	0.0919 (10)
H11A	0.4255	0.1626	1.2352	0.138*
H11B	0.4337	0.2778	1.1734	0.138*
H11C	0.5646	0.1720	1.1865	0.138*
C12	0.4469 (5)	−0.0790 (3)	1.15008 (15)	0.1004 (11)
H12A	0.5481	−0.0858	1.1376	0.151*
H12B	0.3920	−0.1468	1.1218	0.151*
H12C	0.4347	−0.1008	1.2002	0.151*
C13	0.2279 (3)	0.0833 (4)	1.13551 (16)	0.0914 (10)
H13A	0.1880	0.0102	1.1045	0.137*
H13B	0.1989	0.1772	1.1186	0.137*
H13C	0.1924	0.0692	1.1836	0.137*
C14	−0.1016 (3)	−0.0130 (4)	1.00859 (19)	0.0961 (11)
H14A	−0.1445	−0.1076	1.0052	0.144*
H14B	−0.1733	0.0589	0.9969	0.144*
H14C	−0.0670	0.0026	1.0567	0.144*
F1	0.30213 (17)	−0.21153 (14)	0.89103 (8)	0.0696 (4)
N1	0.38966 (18)	−0.00242 (17)	0.99719 (8)	0.0410 (4)
H1	0.3884	−0.0897	1.0133	0.049*
O1	0.02014 (16)	−0.00250 (18)	0.95826 (11)	0.0748 (5)
O2	0.10015 (19)	−0.21952 (17)	0.99189 (10)	0.0648 (5)
O3	0.61290 (18)	0.1341 (2)	1.04867 (11)	0.0792 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0395 (3)	0.0456 (3)	0.0519 (3)	−0.0028 (2)	0.0025 (2)	−0.0062 (2)
C1	0.0440 (11)	0.0485 (11)	0.0438 (11)	−0.0090 (10)	0.0010 (10)	0.0042 (9)
C2	0.0517 (14)	0.0817 (17)	0.0600 (14)	−0.0088 (13)	−0.0025 (11)	0.0254 (13)
C3	0.0740 (19)	0.111 (2)	0.0545 (14)	−0.0187 (18)	0.0034 (13)	0.0315 (15)
C4	0.0731 (19)	0.101 (2)	0.0632 (17)	−0.0250 (17)	0.0232 (15)	0.0080 (16)
C5	0.0572 (15)	0.0885 (19)	0.0832 (18)	0.0025 (15)	0.0285 (13)	0.0076 (16)
C6	0.0578 (14)	0.0670 (14)	0.0595 (14)	0.0055 (12)	0.0115 (11)	0.0130 (12)
C7	0.0402 (10)	0.0416 (10)	0.0418 (10)	−0.0018 (8)	0.0021 (8)	0.0043 (9)
C8	0.0455 (12)	0.0540 (12)	0.0458 (11)	−0.0051 (10)	0.0000 (9)	0.0011 (10)
C9	0.0369 (10)	0.0445 (11)	0.0588 (12)	−0.0058 (8)	−0.0021 (10)	0.0024 (11)
C10	0.0636 (15)	0.0741 (16)	0.0440 (12)	−0.0009 (13)	0.0036 (11)	−0.0078 (11)
C11	0.094 (2)	0.121 (2)	0.0608 (16)	−0.006 (2)	−0.0073 (16)	−0.0322 (16)
C12	0.152 (3)	0.089 (2)	0.0602 (16)	0.007 (2)	−0.020 (2)	0.0179 (15)
C13	0.0664 (18)	0.133 (3)	0.0744 (18)	−0.0155 (18)	0.0280 (15)	−0.0240 (18)
C14	0.0490 (15)	0.0811 (18)	0.158 (3)	0.0062 (14)	0.0448 (19)	0.019 (2)
F1	0.0689 (9)	0.0569 (8)	0.0828 (10)	−0.0086 (7)	0.0215 (7)	−0.0240 (7)
N1	0.0477 (10)	0.0368 (8)	0.0385 (8)	−0.0010 (7)	0.0006 (7)	0.0035 (7)
O1	0.0440 (9)	0.0610 (10)	0.1193 (15)	0.0081 (8)	0.0214 (10)	0.0283 (10)
O2	0.0621 (10)	0.0489 (9)	0.0835 (12)	−0.0020 (7)	0.0163 (9)	0.0133 (9)
O3	0.0401 (8)	0.0993 (14)	0.0981 (13)	−0.0126 (9)	0.0054 (9)	−0.0301 (12)

Geometric parameters (Å, º) top

S1—O3	1.4737 (17)	C8—H8	0.9800
S1—N1	1.6685 (17)	C9—O2	1.199 (2)
S1—C10	1.830 (2)	C9—O1	1.303 (3)
C1—C2	1.381 (3)	C10—C12	1.513 (4)
C1—C6	1.381 (3)	C10—C13	1.518 (4)
C1—C7	1.516 (3)	C10—C11	1.527 (4)
C2—C3	1.381 (4)	C11—H11A	0.9600
C2—H2	0.9300	C11—H11B	0.9600
C3—C4	1.361 (4)	C11—H11C	0.9600
C3—H3	0.9300	C12—H12A	0.9600
C4—C5	1.361 (4)	C12—H12B	0.9600
C4—H4	0.9300	C12—H12C	0.9600
C5—C6	1.382 (3)	C13—H13A	0.9600
C5—H5	0.9300	C13—H13B	0.9600
C6—H6	0.9300	C13—H13C	0.9600
C7—N1	1.458 (2)	C14—O1	1.460 (3)
C7—C8	1.533 (3)	C14—H14A	0.9600
C7—H7	0.9800	C14—H14B	0.9600
C8—F1	1.379 (3)	C14—H14C	0.9600
C8—C9	1.507 (3)	N1—H1	0.8600

O3—S1—N1	110.87 (10)	O1—C9—C8	109.95 (18)
O3—S1—C10	105.74 (12)	C12—C10—C13	112.7 (3)
N1—S1—C10	98.71 (10)	C12—C10—C11	111.1 (2)
C2—C1—C6	117.7 (2)	C13—C10—C11	111.2 (2)
C2—C1—C7	119.5 (2)	C12—C10—S1	111.0 (2)
C6—C1—C7	122.66 (17)	C13—C10—S1	106.35 (19)
C1—C2—C3	120.8 (3)	C11—C10—S1	104.17 (19)
C1—C2—H2	119.6	C10—C11—H11A	109.5
C3—C2—H2	119.6	C10—C11—H11B	109.5
C4—C3—C2	120.6 (3)	H11A—C11—H11B	109.5
C4—C3—H3	119.7	C10—C11—H11C	109.5
C2—C3—H3	119.7	H11A—C11—H11C	109.5
C3—C4—C5	119.4 (2)	H11B—C11—H11C	109.5
C3—C4—H4	120.3	C10—C12—H12A	109.5
C5—C4—H4	120.3	C10—C12—H12B	109.5
C4—C5—C6	120.5 (3)	H12A—C12—H12B	109.5
C4—C5—H5	119.8	C10—C12—H12C	109.5
C6—C5—H5	119.8	H12A—C12—H12C	109.5
C1—C6—C5	120.9 (2)	H12B—C12—H12C	109.5
C1—C6—H6	119.5	C10—C13—H13A	109.5
C5—C6—H6	119.5	C10—C13—H13B	109.5
N1—C7—C1	116.05 (17)	H13A—C13—H13B	109.5
N1—C7—C8	108.22 (16)	C10—C13—H13C	109.5
C1—C7—C8	109.24 (16)	H13A—C13—H13C	109.5
N1—C7—H7	107.7	H13B—C13—H13C	109.5
C1—C7—H7	107.7	O1—C14—H14A	109.5
C8—C7—H7	107.7	O1—C14—H14B	109.5
F1—C8—C9	107.71 (16)	H14A—C14—H14B	109.5
F1—C8—C7	109.26 (18)	O1—C14—H14C	109.5
C9—C8—C7	113.67 (17)	H14A—C14—H14C	109.5
F1—C8—H8	108.7	H14B—C14—H14C	109.5
C9—C8—H8	108.7	C7—N1—S1	116.21 (12)
C7—C8—H8	108.7	C7—N1—H1	121.9
O2—C9—O1	125.5 (2)	S1—N1—H1	121.9
O2—C9—C8	124.6 (2)	C9—O1—C14	116.76 (19)

Hydrogen-bond geometry (Å, º) top

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

Symmetry code: (i) x−1, y, z.

Hydrogen-bond geometry (Å, º) top

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

Symmetry code: (i) x−1, y, z.

Acknowledgements

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

References

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

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

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