N-[(2S)-4-Chloro-2-(l-menth-yloxy)-5-oxo-2,5-dihydro-furan-3-yl]-l-valine.

The title compound, C(19)H(30)ClNO(5), was obtained by the tandem asymmetric Michael addition-elimination reaction of (5S)-3,4-dichloro-5-(l-menth-yloxy)furan-2(5H)-one and l-valine in the presence of potassium hydroxide. The furan-one unit is approximately planar (r.m.s. deviation = 0.0204 Å) and the six-membered cyclo-hexane ring adopts a chair conformation. The crystal structure is stabilized by a network of O-H⋯O and N-H⋯O hydrogen bonds.

Related literature

For biologically active 4-amino-2(5H)-furan­ones, see: Kimura et al. (2000 ▶); Tanoury et al., 2008 ▶). For the synthesis of the precursor, (5S)-3,4-dichloro-5-(l-menth­yloxy)furan-2(5H)-one, see: Chen & Geng (1993 ▶).

Experimental

Crystal data

C19H30ClNO5

M = 387.89

Tetragonal,

a = 10.4540 (4) Å

c = 39.300 (3) Å

V = 4294.9 (4) Å3

Z = 8

Mo Kα radiation

μ = 0.20 mm−1

T = 293 K

0.30 × 0.23 × 0.15 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.769, T max = 0.867 (expected range = 0.860–0.970)

22031 measured reflections

3796 independent reflections

2868 reflections with I > 2σ(I)

R int = 0.053

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.091

S = 1.04

3796 reflections

242 parameters

H-atom parameters constrained

Δρmax = 0.18 e Å−3

Δρmin = −0.23 e Å−3

Absolute structure: Flack, (1983 ▶), 1499 Friedel pairs

Flack parameter: −0.03 (8)

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); 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 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809022120/gk2204sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809022120/gk2204Isup2.hkl

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

C19H30ClNO5	Dx = 1.200 Mg m−3
Mr = 387.89	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P43212	Cell parameters from 3405 reflections
Hall symbol: P 4nw 2abw	θ = 2.2–19.1°
a = 10.4540 (4) Å	µ = 0.20 mm−1
c = 39.300 (3) Å	T = 293 K
V = 4294.9 (4) Å3	Block, colourless
Z = 8	0.30 × 0.23 × 0.15 mm
F(000) = 1664.0

Bruker APEXII CCD area-detector diffractometer	3796 independent reflections
Radiation source: fine-focus sealed tube	2868 reflections with I > 2σ(I)
graphite	Rint = 0.053
Detector resolution: 0 pixels mm-1	θmax = 25.0°, θmin = 2.0°
φ and ω scans	h = −12→10
Absorption correction: multi-scan (SADABS; Bruker, 2004)	k = −11→12
Tmin = 0.769, Tmax = 0.867	l = −46→46
22031 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.040	w = 1/[σ2(Fo2) + (0.0329P)2 + 0.7758P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.091	(Δ/σ)max = 0.001
S = 1.04	Δρmax = 0.18 e Å−3
3796 reflections	Δρmin = −0.23 e Å−3
242 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*^=kFc[1+0.001xFc^2^λ^3^/sin(2θ)]^-1/4^
0 restraints	Extinction coefficient: 0.0020 (3)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack, (1983), 1499 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: −0.03 (8)

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s 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
C1	0.6886 (3)	−0.0142 (2)	−0.02302 (5)	0.0457 (6)
C2	0.6349 (2)	0.0184 (2)	0.01161 (5)	0.0434 (6)
H2	0.5486	−0.0178	0.0132	0.052*
C3	0.6252 (3)	0.1638 (3)	0.01705 (6)	0.0645 (8)
H3	0.6169	0.1771	0.0416	0.077*
C4	0.5046 (4)	0.2198 (3)	0.00080 (9)	0.1066 (14)
H4A	0.4929	0.3061	0.0085	0.160*
H4B	0.4318	0.1692	0.0072	0.160*
H4C	0.5135	0.2191	−0.0235	0.160*
C5	0.7443 (4)	0.2337 (3)	0.00618 (8)	0.0901 (11)
H5A	0.8180	0.1926	0.0158	0.135*
H5B	0.7403	0.3207	0.0140	0.135*
H5C	0.7507	0.2325	−0.0182	0.135*
C6	0.6726 (2)	−0.0701 (2)	0.06900 (5)	0.0420 (6)
C7	0.5557 (2)	−0.0781 (2)	0.08334 (5)	0.0478 (6)
C8	0.5677 (3)	−0.1196 (2)	0.11793 (5)	0.0489 (6)
C9	0.7698 (2)	−0.0992 (2)	0.09642 (5)	0.0429 (6)
H9	0.8263	−0.1695	0.0896	0.052*
C10	0.9662 (2)	−0.0054 (2)	0.11656 (5)	0.0445 (6)
H10	1.0136	−0.0663	0.1024	0.053*
C11	0.9624 (2)	−0.0546 (3)	0.15302 (5)	0.0529 (7)
H11A	0.9221	−0.1381	0.1534	0.063*
H11B	0.9112	0.0029	0.1668	0.063*
C12	1.0967 (3)	−0.0645 (3)	0.16813 (6)	0.0596 (7)
H12	1.1447	−0.1278	0.1549	0.072*
C13	1.0913 (3)	−0.1106 (3)	0.20518 (6)	0.0868 (10)
H13A	1.0524	−0.0458	0.2191	0.130*
H13B	1.1764	−0.1271	0.2132	0.130*
H13C	1.0416	−0.1877	0.2065	0.130*
C14	1.1649 (3)	0.0631 (3)	0.16501 (7)	0.0753 (9)
H14A	1.1233	0.1250	0.1797	0.090*
H14B	1.2525	0.0534	0.1727	0.090*
C15	1.1654 (3)	0.1133 (3)	0.12899 (7)	0.0723 (9)
H15A	1.2151	0.0562	0.1147	0.087*
H15B	1.2062	0.1966	0.1286	0.087*
C16	1.0302 (2)	0.1249 (2)	0.11446 (6)	0.0522 (7)
H16	0.9828	0.1814	0.1299	0.063*
C17	1.0229 (3)	0.1862 (3)	0.07910 (7)	0.0698 (8)
H17	0.9327	0.1846	0.0723	0.084*
C18	1.0627 (4)	0.3269 (3)	0.08046 (11)	0.1295 (16)
H18A	1.0213	0.3678	0.0993	0.194*
H18B	1.0380	0.3685	0.0597	0.194*
H18C	1.1538	0.3325	0.0832	0.194*
C19	1.0969 (4)	0.1145 (4)	0.05192 (7)	0.1001 (12)
H19A	1.1866	0.1177	0.0571	0.150*
H19B	1.0818	0.1534	0.0302	0.150*
H19C	1.0692	0.0270	0.0514	0.150*
Cl1	0.40649 (7)	−0.05720 (10)	0.066293 (16)	0.0818 (3)
N1	0.71379 (18)	−0.0411 (2)	0.03775 (4)	0.0463 (5)
H1	0.7919	−0.0586	0.0327	0.056*
O1	0.60255 (18)	0.0096 (2)	−0.04637 (4)	0.0835 (7)
H1A	0.6322	−0.0068	−0.0652	0.125*
O2	0.79397 (18)	−0.05167 (19)	−0.02856 (4)	0.0633 (5)
O3	0.48370 (18)	−0.14530 (18)	0.13838 (4)	0.0625 (5)
O4	0.69263 (17)	−0.13404 (16)	0.12582 (3)	0.0515 (5)
O5	0.83805 (15)	0.01070 (15)	0.10286 (4)	0.0472 (4)

	U11	U22	U33	U12	U13	U23
C1	0.0580 (17)	0.0518 (16)	0.0274 (11)	0.0057 (12)	−0.0053 (11)	0.0020 (11)
C2	0.0501 (15)	0.0544 (16)	0.0259 (10)	0.0075 (12)	−0.0023 (10)	0.0030 (10)
C3	0.095 (2)	0.0608 (18)	0.0382 (13)	0.0207 (17)	0.0001 (14)	−0.0027 (13)
C4	0.135 (4)	0.086 (3)	0.099 (2)	0.056 (2)	−0.020 (2)	0.002 (2)
C5	0.132 (3)	0.067 (2)	0.072 (2)	−0.014 (2)	0.006 (2)	0.0021 (17)
C6	0.0515 (15)	0.0469 (15)	0.0276 (11)	0.0046 (11)	−0.0012 (11)	−0.0033 (10)
C7	0.0480 (15)	0.0655 (17)	0.0301 (11)	0.0041 (13)	0.0008 (11)	0.0020 (11)
C8	0.0632 (19)	0.0531 (16)	0.0303 (11)	−0.0084 (13)	0.0000 (12)	−0.0034 (11)
C9	0.0542 (15)	0.0481 (15)	0.0265 (11)	−0.0019 (12)	−0.0016 (10)	0.0020 (11)
C10	0.0485 (15)	0.0488 (15)	0.0361 (12)	0.0063 (12)	−0.0051 (11)	−0.0040 (11)
C11	0.0620 (17)	0.0601 (17)	0.0365 (12)	0.0011 (14)	−0.0035 (12)	−0.0009 (12)
C12	0.0670 (18)	0.070 (2)	0.0418 (13)	0.0108 (15)	−0.0119 (13)	−0.0125 (13)
C13	0.106 (3)	0.108 (3)	0.0464 (16)	0.017 (2)	−0.0248 (17)	−0.0055 (17)
C14	0.070 (2)	0.092 (3)	0.0641 (18)	−0.0008 (18)	−0.0196 (15)	−0.0204 (17)
C15	0.064 (2)	0.073 (2)	0.079 (2)	−0.0123 (17)	−0.0053 (16)	−0.0122 (17)
C16	0.0554 (17)	0.0466 (16)	0.0545 (15)	0.0019 (12)	0.0008 (13)	−0.0082 (12)
C17	0.074 (2)	0.0622 (19)	0.0737 (19)	−0.0058 (16)	0.0041 (16)	0.0165 (15)
C18	0.153 (4)	0.071 (3)	0.164 (4)	−0.030 (3)	0.003 (3)	0.035 (3)
C19	0.119 (3)	0.123 (3)	0.0585 (18)	0.011 (3)	0.014 (2)	0.019 (2)
Cl1	0.0488 (4)	0.1483 (8)	0.0483 (4)	0.0136 (5)	0.0026 (3)	0.0132 (4)
N1	0.0460 (12)	0.0683 (14)	0.0247 (9)	0.0099 (10)	0.0023 (8)	0.0061 (9)
O1	0.0698 (13)	0.151 (2)	0.0296 (8)	0.0369 (14)	−0.0086 (9)	−0.0045 (11)
O2	0.0639 (13)	0.0890 (15)	0.0369 (9)	0.0293 (11)	0.0062 (8)	0.0049 (9)
O3	0.0717 (13)	0.0841 (14)	0.0317 (8)	−0.0182 (10)	0.0114 (9)	0.0017 (8)
O4	0.0601 (12)	0.0674 (12)	0.0270 (8)	−0.0094 (9)	−0.0030 (8)	0.0084 (7)
O5	0.0530 (11)	0.0463 (11)	0.0422 (9)	0.0000 (8)	−0.0070 (8)	0.0009 (8)

C1—O2	1.189 (3)	C11—C12	1.528 (3)
C1—O1	1.309 (3)	C11—H11A	0.9700
C1—C2	1.511 (3)	C11—H11B	0.9700
C2—N1	1.456 (3)	C12—C14	1.517 (4)
C2—C3	1.538 (3)	C12—C13	1.534 (3)
C2—H2	0.9800	C12—H12	0.9800
C3—C5	1.506 (4)	C13—H13A	0.9600
C3—C4	1.530 (4)	C13—H13B	0.9600
C3—H3	0.9800	C13—H13C	0.9600
C4—H4A	0.9600	C14—C15	1.510 (4)
C4—H4B	0.9600	C14—H14A	0.9700
C4—H4C	0.9600	C14—H14B	0.9700
C5—H5A	0.9600	C15—C16	1.529 (4)
C5—H5B	0.9600	C15—H15A	0.9700
C5—H5C	0.9600	C15—H15B	0.9700
C6—N1	1.336 (3)	C16—C17	1.532 (3)
C6—C7	1.348 (3)	C16—H16	0.9800
C6—C9	1.511 (3)	C17—C19	1.518 (4)
C7—C8	1.432 (3)	C17—C18	1.529 (4)
C7—Cl1	1.712 (2)	C17—H17	0.9800
C8—O3	1.220 (3)	C18—H18A	0.9600
C8—O4	1.351 (3)	C18—H18B	0.9600
C9—O5	1.376 (3)	C18—H18C	0.9600
C9—O4	1.455 (3)	C19—H19A	0.9600
C9—H9	0.9800	C19—H19B	0.9600
C10—O5	1.454 (3)	C19—H19C	0.9600
C10—C16	1.520 (3)	N1—H1	0.8600
C10—C11	1.523 (3)	O1—H1A	0.8200
C10—H10	0.9800
O2—C1—O1	124.8 (2)	C14—C12—C11	109.9 (2)
O2—C1—C2	125.7 (2)	C14—C12—C13	111.7 (2)
O1—C1—C2	109.5 (2)	C11—C12—C13	110.9 (2)
N1—C2—C1	109.21 (18)	C14—C12—H12	108.1
N1—C2—C3	111.14 (19)	C11—C12—H12	108.1
C1—C2—C3	111.9 (2)	C13—C12—H12	108.1
N1—C2—H2	108.2	C12—C13—H13A	109.5
C1—C2—H2	108.2	C12—C13—H13B	109.5
C3—C2—H2	108.2	H13A—C13—H13B	109.5
C5—C3—C4	112.2 (3)	C12—C13—H13C	109.5
C5—C3—C2	112.7 (2)	H13A—C13—H13C	109.5
C4—C3—C2	112.0 (2)	H13B—C13—H13C	109.5
C5—C3—H3	106.5	C15—C14—C12	112.5 (2)
C4—C3—H3	106.5	C15—C14—H14A	109.1
C2—C3—H3	106.5	C12—C14—H14A	109.1
C3—C4—H4A	109.5	C15—C14—H14B	109.1
C3—C4—H4B	109.5	C12—C14—H14B	109.1
H4A—C4—H4B	109.5	H14A—C14—H14B	107.8
C3—C4—H4C	109.5	C14—C15—C16	112.0 (2)
H4A—C4—H4C	109.5	C14—C15—H15A	109.2
H4B—C4—H4C	109.5	C16—C15—H15A	109.2
C3—C5—H5A	109.5	C14—C15—H15B	109.2
C3—C5—H5B	109.5	C16—C15—H15B	109.2
H5A—C5—H5B	109.5	H15A—C15—H15B	107.9
C3—C5—H5C	109.5	C10—C16—C15	108.4 (2)
H5A—C5—H5C	109.5	C10—C16—C17	113.7 (2)
H5B—C5—H5C	109.5	C15—C16—C17	114.7 (2)
N1—C6—C7	133.7 (2)	C10—C16—H16	106.5
N1—C6—C9	119.0 (2)	C15—C16—H16	106.5
C7—C6—C9	107.34 (18)	C17—C16—H16	106.5
C6—C7—C8	109.7 (2)	C19—C17—C18	111.2 (3)
C6—C7—Cl1	130.86 (17)	C19—C17—C16	114.0 (2)
C8—C7—Cl1	119.30 (18)	C18—C17—C16	110.9 (3)
O3—C8—O4	121.3 (2)	C19—C17—H17	106.8
O3—C8—C7	129.0 (2)	C18—C17—H17	106.8
O4—C8—C7	109.6 (2)	C16—C17—H17	106.8
O5—C9—O4	110.51 (17)	C17—C18—H18A	109.5
O5—C9—C6	108.15 (19)	C17—C18—H18B	109.5
O4—C9—C6	104.14 (18)	H18A—C18—H18B	109.5
O5—C9—H9	111.3	C17—C18—H18C	109.5
O4—C9—H9	111.3	H18A—C18—H18C	109.5
C6—C9—H9	111.3	H18B—C18—H18C	109.5
O5—C10—C16	106.35 (18)	C17—C19—H19A	109.5
O5—C10—C11	111.29 (19)	C17—C19—H19B	109.5
C16—C10—C11	111.45 (19)	H19A—C19—H19B	109.5
O5—C10—H10	109.2	C17—C19—H19C	109.5
C16—C10—H10	109.2	H19A—C19—H19C	109.5
C11—C10—H10	109.2	H19B—C19—H19C	109.5
C10—C11—C12	111.4 (2)	C6—N1—C2	124.25 (19)
C10—C11—H11A	109.4	C6—N1—H1	117.9
C12—C11—H11A	109.4	C2—N1—H1	117.9
C10—C11—H11B	109.4	C1—O1—H1A	109.5
C12—C11—H11B	109.4	C8—O4—C9	109.00 (16)
H11A—C11—H11B	108.0	C9—O5—C10	116.73 (18)
O2—C1—C2—N1	−18.5 (4)	C13—C12—C14—C15	−177.1 (3)
O1—C1—C2—N1	163.8 (2)	C12—C14—C15—C16	56.1 (3)
O2—C1—C2—C3	105.0 (3)	O5—C10—C16—C15	179.41 (19)
O1—C1—C2—C3	−72.8 (3)	C11—C10—C16—C15	58.0 (3)
N1—C2—C3—C5	76.6 (3)	O5—C10—C16—C17	−51.8 (3)
C1—C2—C3—C5	−45.8 (3)	C11—C10—C16—C17	−173.2 (2)
N1—C2—C3—C4	−155.9 (2)	C14—C15—C16—C10	−56.8 (3)
C1—C2—C3—C4	81.8 (3)	C14—C15—C16—C17	175.0 (2)
N1—C6—C7—C8	177.3 (3)	C10—C16—C17—C19	−65.7 (3)
C9—C6—C7—C8	−4.1 (3)	C15—C16—C17—C19	59.8 (3)
N1—C6—C7—Cl1	1.9 (4)	C10—C16—C17—C18	167.9 (3)
C9—C6—C7—Cl1	−179.5 (2)	C15—C16—C17—C18	−66.5 (4)
C6—C7—C8—O3	−175.2 (3)	C7—C6—N1—C2	14.1 (4)
Cl1—C7—C8—O3	0.9 (4)	C9—C6—N1—C2	−164.4 (2)
C6—C7—C8—O4	1.9 (3)	C1—C2—N1—C6	−155.7 (2)
Cl1—C7—C8—O4	177.94 (17)	C3—C2—N1—C6	80.5 (3)
N1—C6—C9—O5	66.0 (3)	O3—C8—O4—C9	178.6 (2)
C7—C6—C9—O5	−112.9 (2)	C7—C8—O4—C9	1.3 (3)
N1—C6—C9—O4	−176.5 (2)	O5—C9—O4—C8	112.3 (2)
C7—C6—C9—O4	4.7 (3)	C6—C9—O4—C8	−3.6 (2)
O5—C10—C11—C12	−176.8 (2)	O4—C9—O5—C10	92.0 (2)
C16—C10—C11—C12	−58.3 (3)	C6—C9—O5—C10	−154.55 (17)
C10—C11—C12—C14	54.4 (3)	C16—C10—O5—C9	168.55 (17)
C10—C11—C12—C13	178.4 (2)	C11—C10—O5—C9	−69.9 (2)
C11—C12—C14—C15	−53.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O2i	0.86	2.25	3.019 (3)	148
O1—H1A···O3ii	0.82	1.83	2.617 (2)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2i	0.86	2.25	3.019 (3)	148
O1—H1A⋯O3ii	0.82	1.83	2.617 (2)	160

Symmetry codes: (i) ; (ii) .