N-{4-Bromo-2-[(S)-menth-yloxy]-5-oxo-2,5-dihydro-3-fur-yl}-l-valine.

The title compound, C(19)H(30)BrNO(5), was obtained via a tandem asymmetric Michael addition-elimination reaction of 3,4-dibromo-5-[(S)-l-menth-yloxy]furan-2(5H)-one and l-valine in the presence of potassium hydroxide. The mol-ecular structure contains an approximately planar (r.m.s. deviation = 0.0204 Å) five-membered furan-one ring and a six-membered menth-yloxy ring adopting a chair conformation. The crystal packing is stabilized by inter-molecular O-H⋯O and N-H⋯O hydrogen bonding.

Related literature

For applications of chiral 5-(l-menth­yloxy)-2(5H)-furan­ones, see: Feringa & De Jong (1988 ▶); De Koning et al. (1997 ▶); Lattmann et al. (1999 ▶); He et al. (2006 ▶); Wang et al. (2006 ▶). For biologically active 4-amino-2(5H)-furan­ones, see: Kimura et al. (2000 ▶); Tanoury et al. (2008 ▶). For related compounds, see: Wang et al. (2006 ▶); Li et al. (2009 ▶). For the synthesis, see: Chen & Geng (1993 ▶).

Experimental

Crystal data

C19H30BrNO5

M = 432.34

Tetragonal,

a = 10.5409 (9) Å

c = 39.388 (7) Å

V = 4376.4 (9) Å3

Z = 8

Mo Kα radiation

μ = 1.91 mm−1

T = 293 K

0.30 × 0.22 × 0.18 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T min = 0.558, T max = 0.710

22304 measured reflections

3859 independent reflections

2726 reflections with I > 2σ(I)

R int = 0.065

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.085

S = 1.03

3859 reflections

241 parameters

H-atom parameters constrained

Δρmax = 0.43 e Å−3

Δρmin = −0.40 e Å−3

Absolute structure: Flack (1983 ▶), 1526 Friedel pairs

Flack parameter: −0.001 (11)

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809026129/xu2542sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809026129/xu2542Isup2.hkl

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

C19H30BrNO5	Dx = 1.312 Mg m−3
Mr = 432.34	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P43212	Cell parameters from 3973 reflections
Hall symbol: P 4nw 2abw	θ = 2.2–19.3°
a = 10.5409 (9) Å	µ = 1.91 mm−1
c = 39.388 (7) Å	T = 293 K
V = 4376.4 (9) Å3	Block, colourless
Z = 8	0.30 × 0.22 × 0.18 mm
F(000) = 1808.0

Bruker APEXII area-detector diffractometer	3859 independent reflections
Radiation source: fine-focus sealed tube	2726 reflections with I > 2σ(I)
graphite	Rint = 0.065
φ and ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 2004)	h = −11→12
Tmin = 0.558, Tmax = 0.710	k = −12→9
22304 measured reflections	l = −40→46

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040	H-atom parameters constrained
wR(F2) = 0.085	w = 1/[σ2(Fo2) + (0.0221P)2 + 1.5196P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
3859 reflections	Δρmax = 0.43 e Å−3
241 parameters	Δρmin = −0.40 e Å−3
0 restraints	Absolute structure: Flack (1983), 1526 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: −0.001 (11)

Experimental. Data for (I): [α]20°D = 63.39° (c 0.437, CH3CH2OH); 1H NMR (400 MHz, CDCl3, TMS): 0.830 (3H, d, J = 6.8 Hz, CH3), 0.897–0.933 (7H, m, CH, 2CH3), 0.955–1.047 (8H, m, 2CH3, CH2), 1.316–1.451 (2H, m, 2CH), 1.610–1.708 (2H, m, CH2), 2.102–2.347 (3H, m, CH2, CH), 3.519–3.610 (1H, m, CH), 4.796 (1H, s, NH), 5.160–5.260 (1H, m, CH), 5.720 (1H, s, CH), 10.720 (1H, s, COOH); ESI-MS, m/z (%): Calcd for C19H31BrNO5+([M+H]+): 434.14, Found: 434.16 (95.0).

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 > σ(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.

	x	y	z	Uiso*/Ueq
Br1	0.60721 (4)	1.06205 (6)	0.066070 (11)	0.0784 (2)
C1	0.3102 (4)	1.0150 (4)	−0.02299 (8)	0.0413 (9)
C2	0.3657 (3)	0.9857 (3)	0.01146 (8)	0.0421 (9)
H2	0.4503	1.0240	0.0126	0.051*
C3	0.3802 (4)	0.8413 (4)	0.01711 (9)	0.0599 (12)
H3	0.3900	0.8288	0.0416	0.072*
C4	0.4988 (5)	0.7874 (5)	0.00061 (13)	0.105 (2)
H4A	0.5138	0.7032	0.0090	0.157*
H4B	0.5702	0.8404	0.0060	0.157*
H4C	0.4875	0.7845	−0.0236	0.157*
C5	0.3284 (3)	1.0733 (3)	0.06891 (8)	0.0367 (8)
C6	0.4445 (3)	1.0829 (3)	0.08348 (8)	0.0447 (9)
C7	0.4303 (4)	1.1255 (3)	0.11806 (8)	0.0457 (9)
C8	0.2303 (3)	1.1000 (4)	0.09637 (7)	0.0398 (8)
H8	0.1722	1.1677	0.0894	0.048*
C9	0.0390 (3)	1.0016 (3)	0.11682 (8)	0.0410 (9)
H9	−0.0103	1.0597	0.1026	0.049*
C10	−0.0201 (4)	0.8704 (3)	0.11490 (10)	0.0522 (11)
H10	0.0288	0.8163	0.1303	0.063*
C11	−0.0114 (5)	0.8091 (4)	0.07965 (11)	0.0685 (13)
H11	0.0778	0.8134	0.0728	0.082*
C12	−0.1550 (4)	0.8779 (5)	0.12957 (12)	0.0746 (14)
H12A	−0.2064	0.9322	0.1152	0.090*
H12B	−0.1925	0.7939	0.1294	0.090*
C13	−0.1566 (4)	0.9290 (5)	0.16525 (11)	0.0748 (14)
H13A	−0.1137	0.8694	0.1801	0.090*
H13B	−0.2438	0.9361	0.1728	0.090*
C14	−0.0928 (4)	1.0580 (4)	0.16822 (9)	0.0602 (11)
H14	−0.1425	1.1186	0.1548	0.072*
C15	0.0400 (3)	1.0516 (4)	0.15277 (9)	0.0504 (10)
H15A	0.0772	1.1358	0.1529	0.061*
H15B	0.0929	0.9972	0.1667	0.061*
C16	−0.0907 (5)	1.1053 (5)	0.20473 (10)	0.0854 (15)
H16A	−0.1760	1.1192	0.2124	0.128*
H16B	−0.0441	1.1835	0.2059	0.128*
H16C	−0.0506	1.0431	0.2189	0.128*
C17	0.2621 (5)	0.7689 (5)	0.00673 (12)	0.0897 (16)
H17A	0.2539	0.7706	−0.0175	0.134*
H17B	0.1889	0.8078	0.0169	0.134*
H17C	0.2687	0.6826	0.0143	0.134*
C18	−0.0868 (5)	0.8769 (5)	0.05239 (12)	0.0987 (18)
H18A	−0.0734	0.8358	0.0309	0.148*
H18B	−0.0595	0.9636	0.0510	0.148*
H18C	−0.1754	0.8743	0.0580	0.148*
C19	−0.0465 (6)	0.6681 (5)	0.08090 (16)	0.123 (2)
H19A	−0.1369	0.6595	0.0827	0.185*
H19B	−0.0070	0.6294	0.1003	0.185*
H19C	−0.0175	0.6271	0.0606	0.185*
N1	0.2878 (3)	1.0434 (3)	0.03785 (6)	0.0450 (7)
H1	0.2098	1.0594	0.0330	0.054*
O1	0.3055 (3)	1.1382 (2)	0.12568 (5)	0.0479 (7)
O2	0.5122 (3)	1.1529 (3)	0.13854 (6)	0.0604 (8)
O3	0.1660 (2)	0.9901 (2)	0.10285 (6)	0.0429 (6)
O4	0.3943 (3)	0.9922 (4)	−0.04650 (6)	0.0843 (11)
H4	0.3630	1.0057	−0.0652	0.127*
O5	0.2048 (3)	1.0509 (3)	−0.02793 (6)	0.0596 (8)

	U11	U22	U33	U12	U13	U23
Br1	0.0465 (2)	0.1398 (5)	0.0488 (2)	0.0113 (3)	−0.0033 (2)	−0.0117 (3)
C1	0.047 (2)	0.051 (2)	0.0254 (19)	0.0110 (19)	−0.0007 (17)	−0.0051 (16)
C2	0.046 (2)	0.054 (3)	0.0255 (18)	0.0083 (18)	−0.0002 (15)	−0.0037 (16)
C3	0.093 (3)	0.058 (3)	0.029 (2)	0.023 (2)	−0.006 (2)	0.0020 (18)
C4	0.136 (5)	0.091 (4)	0.087 (4)	0.056 (4)	0.017 (4)	−0.007 (3)
C5	0.050 (2)	0.038 (2)	0.0221 (18)	0.0055 (18)	0.0006 (16)	0.0007 (15)
C6	0.052 (2)	0.057 (3)	0.0252 (17)	−0.002 (2)	−0.0005 (17)	0.0033 (16)
C7	0.061 (3)	0.050 (2)	0.0257 (18)	−0.010 (2)	−0.0028 (19)	0.0072 (17)
C8	0.051 (2)	0.044 (2)	0.0246 (18)	−0.001 (2)	0.0024 (16)	−0.0045 (18)
C9	0.042 (2)	0.047 (2)	0.034 (2)	0.004 (2)	0.0062 (17)	0.0082 (16)
C10	0.051 (3)	0.051 (3)	0.054 (2)	−0.004 (2)	−0.003 (2)	0.0120 (19)
C11	0.068 (3)	0.052 (3)	0.086 (4)	−0.004 (2)	−0.003 (3)	−0.018 (2)
C12	0.060 (3)	0.081 (3)	0.083 (4)	−0.016 (3)	0.007 (2)	0.014 (3)
C13	0.064 (3)	0.098 (4)	0.062 (3)	−0.004 (3)	0.018 (2)	0.019 (3)
C14	0.066 (3)	0.072 (3)	0.043 (2)	0.013 (3)	0.014 (2)	0.014 (2)
C15	0.058 (2)	0.058 (2)	0.035 (2)	0.000 (2)	0.0067 (18)	0.0044 (18)
C16	0.108 (4)	0.099 (4)	0.049 (3)	0.016 (4)	0.030 (3)	0.006 (3)
C17	0.132 (5)	0.068 (3)	0.070 (4)	−0.016 (3)	−0.010 (3)	−0.004 (3)
C18	0.121 (5)	0.114 (4)	0.061 (3)	0.016 (4)	−0.021 (3)	−0.026 (3)
C19	0.129 (5)	0.064 (3)	0.177 (6)	−0.020 (4)	−0.007 (4)	−0.038 (4)
N1	0.0439 (17)	0.066 (2)	0.0249 (15)	0.0106 (16)	−0.0028 (13)	−0.0058 (15)
O1	0.0584 (18)	0.0629 (19)	0.0225 (12)	−0.0081 (13)	0.0048 (12)	−0.0114 (12)
O2	0.070 (2)	0.082 (2)	0.0288 (14)	−0.0203 (15)	−0.0116 (14)	−0.0017 (13)
O3	0.0499 (15)	0.0424 (16)	0.0364 (14)	−0.0019 (13)	0.0063 (12)	−0.0002 (11)
O4	0.0685 (19)	0.158 (3)	0.0264 (14)	0.041 (2)	0.0074 (14)	0.0028 (16)
O5	0.0627 (19)	0.083 (2)	0.0334 (15)	0.0299 (17)	−0.0063 (12)	−0.0061 (14)

Br1—C6	1.861 (4)	C11—C18	1.515 (6)
C1—O5	1.190 (4)	C11—C19	1.532 (6)
C1—O4	1.304 (4)	C11—H11	0.9800
C1—C2	1.509 (4)	C12—C13	1.505 (6)
C2—N1	1.458 (4)	C12—H12A	0.9700
C2—C3	1.546 (5)	C12—H12B	0.9700
C2—H2	0.9800	C13—C14	1.522 (6)
C3—C17	1.516 (6)	C13—H13A	0.9700
C3—C4	1.519 (6)	C13—H13B	0.9700
C3—H3	0.9800	C14—C16	1.522 (5)
C4—H4A	0.9600	C14—C15	1.528 (5)
C4—H4B	0.9600	C14—H14	0.9800
C4—H4C	0.9600	C15—H15A	0.9700
C5—N1	1.334 (4)	C15—H15B	0.9700
C5—C6	1.355 (5)	C16—H16A	0.9600
C5—C8	1.523 (4)	C16—H16B	0.9600
C6—C7	1.442 (4)	C16—H16C	0.9600
C7—O2	1.217 (4)	C17—H17A	0.9600
C7—O1	1.356 (4)	C17—H17B	0.9600
C8—O3	1.366 (4)	C17—H17C	0.9600
C8—O1	1.457 (4)	C18—H18A	0.9600
C8—H8	0.9800	C18—H18B	0.9600
C9—O3	1.452 (4)	C18—H18C	0.9600
C9—C15	1.511 (5)	C19—H19A	0.9600
C9—C10	1.518 (5)	C19—H19B	0.9600
C9—H9	0.9800	C19—H19C	0.9600
C10—C11	1.535 (5)	N1—H1	0.8600
C10—C12	1.537 (6)	O4—H4	0.8200
C10—H10	0.9800
O5—C1—O4	125.2 (3)	C13—C12—C10	112.3 (4)
O5—C1—C2	125.0 (3)	C13—C12—H12A	109.1
O4—C1—C2	109.7 (3)	C10—C12—H12A	109.1
N1—C2—C1	109.7 (3)	C13—C12—H12B	109.1
N1—C2—C3	111.4 (3)	C10—C12—H12B	109.1
C1—C2—C3	111.7 (3)	H12A—C12—H12B	107.9
N1—C2—H2	108.0	C12—C13—C14	112.7 (3)
C1—C2—H2	108.0	C12—C13—H13A	109.0
C3—C2—H2	108.0	C14—C13—H13A	109.0
C17—C3—C4	111.9 (4)	C12—C13—H13B	109.0
C17—C3—C2	112.0 (4)	C14—C13—H13B	109.0
C4—C3—C2	112.8 (4)	H13A—C13—H13B	107.8
C17—C3—H3	106.5	C13—C14—C16	111.8 (3)
C4—C3—H3	106.5	C13—C14—C15	109.5 (3)
C2—C3—H3	106.5	C16—C14—C15	112.2 (4)
C3—C4—H4A	109.5	C13—C14—H14	107.7
C3—C4—H4B	109.5	C16—C14—H14	107.7
H4A—C4—H4B	109.5	C15—C14—H14	107.7
C3—C4—H4C	109.5	C9—C15—C14	112.5 (3)
H4A—C4—H4C	109.5	C9—C15—H15A	109.1
H4B—C4—H4C	109.5	C14—C15—H15A	109.1
N1—C5—C6	134.1 (3)	C9—C15—H15B	109.1
N1—C5—C8	118.5 (3)	C14—C15—H15B	109.1
C6—C5—C8	107.4 (3)	H15A—C15—H15B	107.8
C5—C6—C7	109.3 (3)	C14—C16—H16A	109.5
C5—C6—Br1	131.9 (2)	C14—C16—H16B	109.5
C7—C6—Br1	118.7 (3)	H16A—C16—H16B	109.5
O2—C7—O1	121.2 (3)	C14—C16—H16C	109.5
O2—C7—C6	128.8 (4)	H16A—C16—H16C	109.5
O1—C7—C6	109.9 (3)	H16B—C16—H16C	109.5
O3—C8—O1	110.9 (3)	C3—C17—H17A	109.5
O3—C8—C5	108.3 (3)	C3—C17—H17B	109.5
O1—C8—C5	104.1 (3)	H17A—C17—H17B	109.5
O3—C8—H8	111.1	C3—C17—H17C	109.5
O1—C8—H8	111.1	H17A—C17—H17C	109.5
C5—C8—H8	111.1	H17B—C17—H17C	109.5
O3—C9—C15	112.2 (3)	C11—C18—H18A	109.5
O3—C9—C10	106.5 (3)	C11—C18—H18B	109.5
C15—C9—C10	111.6 (3)	H18A—C18—H18B	109.5
O3—C9—H9	108.9	C11—C18—H18C	109.5
C15—C9—H9	108.9	H18A—C18—H18C	109.5
C10—C9—H9	108.9	H18B—C18—H18C	109.5
C9—C10—C11	113.9 (3)	C11—C19—H19A	109.5
C9—C10—C12	108.3 (3)	C11—C19—H19B	109.5
C11—C10—C12	114.6 (4)	H19A—C19—H19B	109.5
C9—C10—H10	106.5	C11—C19—H19C	109.5
C11—C10—H10	106.5	H19A—C19—H19C	109.5
C12—C10—H10	106.5	H19B—C19—H19C	109.5
C18—C11—C19	110.7 (4)	C5—N1—C2	124.9 (3)
C18—C11—C10	114.3 (4)	C5—N1—H1	117.6
C19—C11—C10	111.4 (4)	C2—N1—H1	117.6
C18—C11—H11	106.6	C7—O1—C8	108.9 (2)
C19—C11—H11	106.6	C8—O3—C9	117.2 (2)
C10—C11—H11	106.6	C1—O4—H4	109.5
O5—C1—C2—N1	−17.4 (5)	C12—C10—C11—C18	60.0 (5)
O4—C1—C2—N1	164.1 (3)	C9—C10—C11—C19	168.0 (4)
O5—C1—C2—C3	106.6 (4)	C12—C10—C11—C19	−66.5 (5)
O4—C1—C2—C3	−71.9 (4)	C9—C10—C12—C13	−56.3 (5)
N1—C2—C3—C17	76.8 (4)	C11—C10—C12—C13	175.3 (4)
C1—C2—C3—C17	−46.2 (4)	C10—C12—C13—C14	55.7 (5)
N1—C2—C3—C4	−155.9 (3)	C12—C13—C14—C16	−177.6 (4)
C1—C2—C3—C4	81.1 (4)	C12—C13—C14—C15	−52.6 (5)
N1—C5—C6—C7	177.2 (4)	O3—C9—C15—C14	−177.3 (3)
C8—C5—C6—C7	−5.1 (4)	C10—C9—C15—C14	−57.9 (4)
N1—C5—C6—Br1	1.8 (6)	C13—C14—C15—C9	53.7 (4)
C8—C5—C6—Br1	179.5 (3)	C16—C14—C15—C9	178.5 (3)
C5—C6—C7—O2	−174.9 (4)	C6—C5—N1—C2	13.4 (6)
Br1—C6—C7—O2	1.2 (5)	C8—C5—N1—C2	−164.1 (3)
C5—C6—C7—O1	2.2 (4)	C1—C2—N1—C5	−156.4 (3)
Br1—C6—C7—O1	178.3 (2)	C3—C2—N1—C5	79.5 (4)
N1—C5—C8—O3	66.1 (4)	O2—C7—O1—C8	179.3 (3)
C6—C5—C8—O3	−112.0 (3)	C6—C7—O1—C8	1.9 (4)
N1—C5—C8—O1	−175.8 (3)	O3—C8—O1—C7	111.4 (3)
C6—C5—C8—O1	6.1 (4)	C5—C8—O1—C7	−4.8 (4)
O3—C9—C10—C11	−51.4 (4)	O1—C8—O3—C9	91.0 (3)
C15—C9—C10—C11	−174.1 (3)	C5—C8—O3—C9	−155.3 (3)
O3—C9—C10—C12	179.8 (3)	C15—C9—O3—C8	−68.8 (3)
C15—C9—C10—C12	57.1 (4)	C10—C9—O3—C8	168.9 (3)
C9—C10—C11—C18	−65.5 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O5i	0.86	2.28	3.047 (4)	149
O4—H4···O2ii	0.82	1.83	2.615 (3)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O5i	0.86	2.28	3.047 (4)	149
O4—H4⋯O2ii	0.82	1.83	2.615 (3)	160

Symmetry codes: (i) ; (ii) .