N-[(2S)-4-Chloro-2-(l-menthyloxy)-5-oxo-2,5-dihydro-3-furyl]-l-alanine.

The title compound, C(17)H(26)ClNO(5), was prepared via a tandem asymmetric Michael addition-elimination reaction of (5S)-3,4-dichloro-5-(l-menth-yloxy)furan-2(5H)--one and l-alanine in the presence of potassium hydroxide. The five-membered furan-one ring is approximately planar while the six-membered menth-yloxy ring adopts a chair conformation. The crystal packing is stabilized by inter-molecular O-H⋯O and N-H⋯O hydrogen bonds.

Related literature

For chiral 5-(l-menth­yloxy)furan-2(5H)-­ones as key building blocks in the synthesis of supra­molecules and important natural products, see: Feringa & De Jong (1988 ▶); He et al. (2006 ▶); Lattmann et al. (1999 ▶). For the use of 4-aminofuran-2(5H)-one in chemical, pharmaceutical and agrochemical research, see: Kimura et al. (2000 ▶); Tanoury et al. (2008 ▶). For a related structure, see: Wang et al. (2008 ▶). For the synthesis of the chiral synthon (5S)-3,4-dichloro-5-(l-menth­yloxy)furan-2(5H)-one, see: Chen & Geng (1993 ▶).

Experimental

Crystal data

C17H26ClNO5

M = 359.84

Orthorhombic,

a = 11.2481 (15) Å

b = 19.642 (2) Å

c = 9.0668 (11) Å

V = 2003.1 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.21 mm−1

T = 293 K

0.30 × 0.23 × 0.18 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T min = 0.761, T max = 0.846 (expected range = 0.866–0.962)

10244 measured reflections

3534 independent reflections

2879 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.046

wR(F 2) = 0.120

S = 1.08

3534 reflections

222 parameters

312 restraints

H-atom parameters constrained

Δρmax = 0.33 e Å−3

Δρmin = −0.34 e Å−3

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

Flack parameter: 0.00 (10)

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: 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: XP in SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809012720/bq2134sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809012720/bq2134Isup2.hkl

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

C17H26ClNO5	F(000) = 768.0
Mr = 359.84	Dx = 1.193 Mg m−3
Orthorhombic, P21212	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2 2ab	Cell parameters from 2460 reflections
a = 11.2481 (15) Å	θ = 2.3–20.5°
b = 19.642 (2) Å	µ = 0.21 mm−1
c = 9.0668 (11) Å	T = 293 K
V = 2003.1 (4) Å3	Block, colorless
Z = 4	0.30 × 0.23 × 0.18 mm

Bruker APEXII area-detector diffractometer	3534 independent reflections
Radiation source: fine-focus sealed tube	2879 reflections with I > 2σ(I)
graphite	Rint = 0.037
ω scan	θmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2004)	h = −13→11
Tmin = 0.761, Tmax = 0.846	k = −23→22
10244 measured reflections	l = −10→7

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)] = 0.046	H-atom parameters constrained
wR(F2) = 0.120	w = 1/[σ2(Fo2) + (0.0567P)2 + 0.3483P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max < 0.001
3534 reflections	Δρmax = 0.33 e Å−3
222 parameters	Δρmin = −0.34 e Å−3
312 restraints	Absolute structure: Flack (1983), 1499 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.00 (10)

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	0.4798 (4)	0.78198 (19)	0.8644 (4)	0.0536 (9)
H1	0.5545	0.7992	0.8232	0.064*
C2	0.4754 (4)	0.79762 (19)	1.0295 (4)	0.0619 (10)
H2	0.3996	0.7797	1.0661	0.074*
C3	0.5733 (5)	0.7571 (2)	1.1058 (6)	0.0907 (13)
H3A	0.6499	0.7742	1.0735	0.109*
H3B	0.5677	0.7645	1.2114	0.109*
C4	0.5674 (6)	0.6817 (2)	1.0753 (6)	0.0968 (14)
H4A	0.6345	0.6594	1.1219	0.116*
H4B	0.4953	0.6633	1.1185	0.116*
C5	0.5686 (6)	0.6664 (2)	0.9133 (6)	0.0897 (13)
H5	0.6455	0.6807	0.8729	0.108*
C6	0.4707 (4)	0.70649 (18)	0.8358 (4)	0.0651 (10)
H6A	0.4756	0.6983	0.7305	0.078*
H6B	0.3940	0.6903	0.8696	0.078*
C7	0.5537 (6)	0.5895 (2)	0.8864 (7)	0.1183 (17)
H7A	0.6122	0.5650	0.9423	0.177*
H7B	0.5640	0.5799	0.7833	0.177*
H7C	0.4756	0.5756	0.9167	0.177*
C8	0.4770 (5)	0.8738 (2)	1.0660 (5)	0.0761 (12)
H8	0.4168	0.8955	1.0038	0.091*
C9	0.4415 (6)	0.8870 (3)	1.2264 (6)	0.1027 (15)
H9A	0.3749	0.8587	1.2517	0.154*
H9B	0.4200	0.9340	1.2381	0.154*
H9C	0.5072	0.8765	1.2900	0.154*
C10	0.5941 (6)	0.9084 (3)	1.0329 (7)	0.1110 (16)
H10A	0.6546	0.8904	1.0967	0.166*
H10B	0.5864	0.9565	1.0491	0.166*
H10C	0.6156	0.9001	0.9321	0.166*
C11	0.3749 (3)	0.81985 (15)	0.6456 (3)	0.0374 (7)
H11	0.4534	0.8277	0.6018	0.045*
C12	0.2880 (3)	0.87618 (15)	0.6067 (3)	0.0347 (7)
C13	0.1874 (3)	0.84593 (15)	0.5583 (4)	0.0383 (7)
C14	0.2086 (3)	0.77365 (15)	0.5426 (4)	0.0393 (7)
C15	0.2405 (3)	0.99911 (15)	0.6191 (4)	0.0427 (8)
H15	0.1863	0.9920	0.5359	0.051*
C16	0.1683 (3)	1.00945 (19)	0.7577 (5)	0.0611 (10)
H16A	0.1188	0.9704	0.7741	0.092*
H16B	0.1193	1.0492	0.7469	0.092*
H16C	0.2208	1.0154	0.8402	0.092*
C17	0.3137 (3)	1.06179 (15)	0.5905 (4)	0.0428 (8)
Cl1	0.04908 (8)	0.87823 (4)	0.51989 (12)	0.0612 (3)
N1	0.3197 (2)	0.94048 (12)	0.6313 (3)	0.0440 (7)
H1A	0.3922	0.9481	0.6563	0.053*
O1	0.3799 (2)	0.81852 (11)	0.7981 (2)	0.0423 (5)
O2	0.31972 (19)	0.75881 (10)	0.5881 (3)	0.0426 (6)
O3	0.1433 (2)	0.72965 (11)	0.4945 (3)	0.0532 (6)
O4	0.2496 (2)	1.10975 (12)	0.5305 (4)	0.0780 (10)
H4	0.2919	1.1427	0.5122	0.117*
O5	0.4163 (2)	1.06720 (11)	0.6217 (3)	0.0610 (7)

	U11	U22	U33	U12	U13	U23
C1	0.061 (2)	0.0474 (17)	0.0526 (19)	0.0069 (16)	−0.0111 (16)	0.0100 (15)
C2	0.080 (2)	0.0552 (19)	0.051 (2)	−0.0053 (18)	−0.0131 (18)	0.0075 (17)
C3	0.120 (3)	0.078 (2)	0.074 (2)	0.009 (2)	−0.036 (2)	0.007 (2)
C4	0.135 (3)	0.074 (3)	0.081 (3)	0.019 (3)	−0.034 (3)	0.021 (2)
C5	0.127 (3)	0.065 (2)	0.077 (3)	0.031 (2)	−0.025 (3)	0.016 (2)
C6	0.094 (3)	0.0458 (19)	0.056 (2)	0.0143 (19)	−0.0131 (19)	0.0062 (16)
C7	0.181 (4)	0.075 (3)	0.099 (3)	0.046 (3)	−0.034 (3)	0.014 (3)
C8	0.102 (3)	0.064 (2)	0.062 (2)	−0.001 (2)	−0.015 (2)	−0.005 (2)
C9	0.141 (4)	0.094 (3)	0.073 (3)	−0.006 (3)	−0.003 (3)	−0.020 (3)
C10	0.137 (4)	0.090 (3)	0.107 (3)	−0.031 (3)	−0.005 (3)	−0.008 (3)
C11	0.0426 (16)	0.0299 (15)	0.0397 (18)	−0.0006 (14)	−0.0029 (14)	0.0015 (13)
C12	0.0369 (15)	0.0272 (14)	0.0401 (17)	−0.0002 (13)	0.0019 (13)	0.0026 (13)
C13	0.0395 (16)	0.0291 (14)	0.0463 (19)	0.0002 (13)	−0.0049 (14)	−0.0001 (14)
C14	0.0437 (18)	0.0324 (16)	0.0418 (19)	−0.0012 (14)	−0.0017 (14)	−0.0025 (14)
C15	0.0397 (16)	0.0267 (15)	0.061 (2)	0.0010 (13)	−0.0075 (15)	0.0044 (15)
C16	0.053 (2)	0.048 (2)	0.083 (3)	−0.0019 (17)	0.0107 (18)	0.0009 (19)
C17	0.0399 (19)	0.0279 (15)	0.061 (2)	0.0008 (14)	−0.0058 (16)	0.0032 (15)
Cl1	0.0444 (5)	0.0433 (5)	0.0960 (8)	0.0070 (4)	−0.0225 (5)	−0.0125 (5)
N1	0.0358 (15)	0.0283 (14)	0.068 (2)	−0.0006 (12)	−0.0108 (14)	0.0035 (13)
O1	0.0457 (13)	0.0385 (12)	0.0426 (14)	0.0057 (10)	−0.0046 (10)	0.0046 (10)
O2	0.0428 (13)	0.0264 (11)	0.0585 (15)	0.0032 (10)	−0.0074 (10)	−0.0051 (10)
O3	0.0541 (14)	0.0321 (12)	0.0734 (17)	−0.0052 (11)	−0.0091 (13)	−0.0130 (12)
O4	0.0509 (15)	0.0357 (14)	0.147 (3)	−0.0056 (12)	−0.0219 (17)	0.0330 (18)
O5	0.0410 (15)	0.0330 (12)	0.109 (2)	−0.0023 (10)	−0.0109 (14)	0.0093 (14)

C1—O1	1.462 (4)	C9—H9C	0.9600
C1—C6	1.509 (5)	C10—H10A	0.9600
C1—C2	1.529 (6)	C10—H10B	0.9600
C1—H1	0.9800	C10—H10C	0.9600
C2—C3	1.524 (6)	C11—O1	1.384 (4)
C2—C8	1.532 (6)	C11—O2	1.447 (4)
C2—H2	0.9800	C11—C12	1.518 (4)
C3—C4	1.509 (6)	C11—H11	0.9800
C3—H3A	0.9700	C12—N1	1.331 (4)
C3—H3B	0.9700	C12—C13	1.351 (4)
C4—C5	1.499 (8)	C13—C14	1.447 (4)
C4—H4A	0.9700	C13—Cl1	1.716 (3)
C4—H4B	0.9700	C14—O3	1.215 (4)
C5—C6	1.525 (6)	C14—O2	1.348 (4)
C5—C7	1.540 (7)	C15—N1	1.460 (4)
C5—H5	0.9800	C15—C17	1.504 (4)
C6—H6A	0.9700	C15—C16	1.510 (5)
C6—H6B	0.9700	C15—H15	0.9800
C7—H7A	0.9600	C16—H16A	0.9600
C7—H7B	0.9600	C16—H16B	0.9600
C7—H7C	0.9600	C16—H16C	0.9600
C8—C10	1.512 (7)	C17—O5	1.193 (4)
C8—C9	1.530 (7)	C17—O4	1.305 (4)
C8—H8	0.9800	N1—H1A	0.8600
C9—H9A	0.9600	O4—H4	0.8200
C9—H9B	0.9600
O1—C1—C6	111.1 (3)	C8—C9—H9A	109.5
O1—C1—C2	106.2 (3)	C8—C9—H9B	109.5
C6—C1—C2	111.3 (3)	H9A—C9—H9B	109.5
O1—C1—H1	109.4	C8—C9—H9C	109.5
C6—C1—H1	109.4	H9A—C9—H9C	109.5
C2—C1—H1	109.4	H9B—C9—H9C	109.5
C3—C2—C1	108.5 (4)	C8—C10—H10A	109.5
C3—C2—C8	113.8 (4)	C8—C10—H10B	109.5
C1—C2—C8	114.0 (3)	H10A—C10—H10B	109.5
C3—C2—H2	106.7	C8—C10—H10C	109.5
C1—C2—H2	106.7	H10A—C10—H10C	109.5
C8—C2—H2	106.7	H10B—C10—H10C	109.5
C4—C3—C2	113.4 (4)	O1—C11—O2	111.2 (2)
C4—C3—H3A	108.9	O1—C11—C12	105.8 (2)
C2—C3—H3A	108.9	O2—C11—C12	104.1 (2)
C4—C3—H3B	108.9	O1—C11—H11	111.8
C2—C3—H3B	108.9	O2—C11—H11	111.8
H3A—C3—H3B	107.7	C12—C11—H11	111.8
C5—C4—C3	112.1 (4)	N1—C12—C13	134.1 (3)
C5—C4—H4A	109.2	N1—C12—C11	118.7 (3)
C3—C4—H4A	109.2	C13—C12—C11	107.1 (3)
C5—C4—H4B	109.2	C12—C13—C14	109.0 (3)
C3—C4—H4B	109.2	C12—C13—Cl1	131.5 (2)
H4A—C4—H4B	107.9	C14—C13—Cl1	119.5 (2)
C4—C5—C6	109.9 (4)	O3—C14—O2	121.1 (3)
C4—C5—C7	110.5 (4)	O3—C14—C13	129.3 (3)
C6—C5—C7	110.8 (5)	O2—C14—C13	109.6 (3)
C4—C5—H5	108.5	N1—C15—C17	109.0 (2)
C6—C5—H5	108.5	N1—C15—C16	111.8 (3)
C7—C5—H5	108.5	C17—C15—C16	109.1 (3)
C1—C6—C5	112.3 (4)	N1—C15—H15	109.0
C1—C6—H6A	109.1	C17—C15—H15	109.0
C5—C6—H6A	109.1	C16—C15—H15	109.0
C1—C6—H6B	109.1	C15—C16—H16A	109.5
C5—C6—H6B	109.1	C15—C16—H16B	109.5
H6A—C6—H6B	107.9	H16A—C16—H16B	109.5
C5—C7—H7A	109.5	C15—C16—H16C	109.5
C5—C7—H7B	109.5	H16A—C16—H16C	109.5
H7A—C7—H7B	109.5	H16B—C16—H16C	109.5
C5—C7—H7C	109.5	O5—C17—O4	124.7 (3)
H7A—C7—H7C	109.5	O5—C17—C15	124.2 (3)
H7B—C7—H7C	109.5	O4—C17—C15	111.1 (3)
C10—C8—C9	109.9 (4)	C12—N1—C15	124.9 (3)
C10—C8—C2	114.0 (4)	C12—N1—H1A	117.5
C9—C8—C2	111.6 (4)	C15—N1—H1A	117.5
C10—C8—H8	107.0	C11—O1—C1	116.8 (3)
C9—C8—H8	107.0	C14—O2—C11	109.2 (2)
C2—C8—H8	107.0	C17—O4—H4	109.5
O1—C1—C2—C3	176.5 (3)	N1—C12—C13—Cl1	−5.9 (6)
C6—C1—C2—C3	55.4 (5)	C11—C12—C13—Cl1	170.3 (3)
O1—C1—C2—C8	−55.6 (5)	C12—C13—C14—O3	−175.4 (3)
C6—C1—C2—C8	−176.7 (4)	Cl1—C13—C14—O3	5.8 (5)
C1—C2—C3—C4	−54.8 (6)	C12—C13—C14—O2	3.1 (4)
C8—C2—C3—C4	177.1 (4)	Cl1—C13—C14—O2	−175.7 (2)
C2—C3—C4—C5	55.4 (7)	N1—C15—C17—O5	−23.0 (5)
C3—C4—C5—C6	−53.4 (7)	C16—C15—C17—O5	99.4 (4)
C3—C4—C5—C7	−176.0 (5)	N1—C15—C17—O4	158.5 (3)
O1—C1—C6—C5	−175.7 (4)	C16—C15—C17—O4	−79.2 (4)
C2—C1—C6—C5	−57.5 (5)	C13—C12—N1—C15	4.8 (6)
C4—C5—C6—C1	55.4 (6)	C11—C12—N1—C15	−171.0 (3)
C7—C5—C6—C1	177.8 (5)	C17—C15—N1—C12	−156.0 (3)
C3—C2—C8—C10	56.0 (6)	C16—C15—N1—C12	83.2 (4)
C1—C2—C8—C10	−69.1 (5)	O2—C11—O1—C1	83.7 (3)
C3—C2—C8—C9	−69.2 (6)	C12—C11—O1—C1	−163.9 (3)
C1—C2—C8—C9	165.7 (4)	C6—C1—O1—C11	−67.5 (4)
O1—C11—C12—N1	69.8 (3)	C2—C1—O1—C11	171.3 (3)
O2—C11—C12—N1	−172.9 (3)	O3—C14—O2—C11	−177.5 (3)
O1—C11—C12—C13	−107.0 (3)	C13—C14—O2—C11	3.8 (3)
O2—C11—C12—C13	10.2 (3)	O1—C11—O2—C14	105.0 (3)
N1—C12—C13—C14	175.6 (3)	C12—C11—O2—C14	−8.4 (3)
C11—C12—C13—C14	−8.2 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O5i	0.86	2.20	2.975 (4)	150
O4—H4···O3ii	0.82	1.86	2.655 (3)	164

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O5i	0.86	2.20	2.975 (4)	150
O4—H4⋯O3ii	0.82	1.86	2.655 (3)	164

Symmetry codes: (i) ; (ii) .