(5S)-3-Chloro-4-(2,5-dihydro-1H-pyrrol-1-yl)-5-[(1R,2S,5R)-2-isopropyl-5-methyl-cyclo-hex-yloxy]furan-2(5H)-one.

The title compound, C(18)H(26)ClNO(3), was obtained via a tandem asymmetric Michael addition-elimination reaction of 3,4-dichloro-5-(S)-(l-menth-yloxy)furan-2(5H)-one and 2,5-di-hydro-1H-pyrrole in the presence of potassium fluoride. In the mol-ecule, the nearly planar dihydro-pyrrole ring [maximum atomic deviation = 0.019 (3) Å] is oriented at a dihedral angle of 10.73 (8)° to the the nearly planar furan-one ring [maximum atomic deviation = 0.011 (2) Å]; the cyclo-hexane ring adopts a chair conformation. In the crystal, mol-ecules are linked via weak inter-molecular C-H⋯O hydrogen bonds, forming supra-molecular chains running along the b axis.

Related literature

The title compound is a derivative of 4-amino-2(5H)-furan­one. For the biological activity of 4-amino-2(5H)-furan­ones, see: Lattmann et al. (1999 ▶, 2005 ▶, 2006 ▶); Rowland et al. (2007 ▶); Kim et al. (2002 ▶). For asymmetric Michael addition reactions of 2(5H)-furan­one, see: He et al. (2006 ▶). For the synthesis of the title compound, see: Song et al. (2009 ▶).

Experimental

Crystal data

C18H26ClNO3

M = 339.85

Orthorhombic,

a = 7.192 (2) Å

b = 9.622 (3) Å

c = 27.534 (9) Å

V = 1905.4 (10) Å3

Z = 4

Mo Kα radiation

μ = 0.21 mm−1

T = 298 K

0.23 × 0.20 × 0.16 mm

Data collection

Bruker APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.952, T max = 0.966

9627 measured reflections

3363 independent reflections

1708 reflections with I > 2σ(I)

R int = 0.053

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.129

S = 1.02

3363 reflections

211 parameters

H-atom parameters constrained

Δρmax = 0.11 e Å−3

Δρmin = −0.14 e Å−3

Absolute structure: Flack (1983 ▶), 1398 Friedel pairs

Flack parameter: 0.14 (12)

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810051226/xu5106sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810051226/xu5106Isup2.hkl

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

C18H26ClNO3	F(000) = 728
Mr = 339.85	Dx = 1.185 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 1222 reflections
a = 7.192 (2) Å	θ = 2.2–17.5°
b = 9.622 (3) Å	µ = 0.21 mm−1
c = 27.534 (9) Å	T = 298 K
V = 1905.4 (10) Å3	Block, colourless
Z = 4	0.23 × 0.20 × 0.16 mm

Bruker APEXII area-detector diffractometer	3363 independent reflections
Radiation source: fine-focus sealed tube	1708 reflections with I > 2σ(I)
graphite	Rint = 0.053
φ and ω scan	θmax = 25.0°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→8
Tmin = 0.952, Tmax = 0.966	k = −10→11
9627 measured reflections	l = −32→28

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)] = 0.052	H-atom parameters constrained
wR(F2) = 0.129	w = 1/[σ2(Fo2) + (0.0439P)2] where P = (Fo2 + 2Fc2)/3
S = 1.02	(Δ/σ)max < 0.001
3363 reflections	Δρmax = 0.11 e Å−3
211 parameters	Δρmin = −0.14 e Å−3
0 restraints	Absolute structure: Flack (1983), 1398 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.14 (12)

Experimental. Data for (I): [α]20°D = -45.0° (c 0.557, CH3CH2OH); 1H NMR (400 MHz, CDCl3, TMS): 0.791 (3H, d, J = 6.8 Hz, CH3), 0.823-0.937 (7H, m, CH, 2CH3), 0.945-1.181 (2H, m, CH2), 1.298-1.457 (2H, m, 2CH), 1.623-1.704 (2H, m, CH2), 2.137-2.210 (2H, m, CH2), 3.576-3.641 (1H, ddd, J = 4.4 Hz, J = 4.4 Hz,J = 4.4 Hz,CH), 3.997-4.970 (4H, m, 2CH2), 5.731-5.884 (3H, m, 3CH), ESI-MS, m/z (%): Calcd for C18H27ClNO3+([M+H]+): 340.16(100.0), 342.16(32.7), Found: 340.24 (100.0), 342.32(38.7).

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.

	x	y	z	Uiso*/Ueq
Cl1	0.78504 (18)	0.24214 (12)	0.34421 (3)	0.1169 (5)
C3	0.7443 (5)	0.2768 (4)	0.24451 (11)	0.0695 (9)
C4	0.7076 (5)	0.1802 (4)	0.20226 (12)	0.0744 (10)
H4	0.5952	0.2084	0.1847	0.089*
C5	0.8243 (6)	0.1400 (4)	0.12119 (10)	0.0775 (11)
H5	0.7375	0.2071	0.1070	0.093*
C1	0.7075 (6)	0.0576 (5)	0.27315 (13)	0.0840 (11)
C2	0.7477 (5)	0.1979 (4)	0.28492 (11)	0.0773 (10)
C6	1.0128 (6)	0.1530 (5)	0.09539 (12)	0.0901 (13)
H6	1.0961	0.0856	0.1108	0.108*
C10	0.7420 (7)	−0.0036 (4)	0.11707 (11)	0.1015 (13)
H10A	0.6212	−0.0050	0.1327	0.122*
H10B	0.8216	−0.0695	0.1338	0.122*
C7	0.9896 (8)	0.1062 (5)	0.04242 (13)	0.1185 (18)
H7A	0.9093	0.1714	0.0256	0.142*
H7B	1.1099	0.1076	0.0265	0.142*
C11	1.1050 (6)	0.2946 (6)	0.10072 (14)	0.1047 (15)
H11	1.0932	0.3206	0.1350	0.126*
C9	0.7204 (10)	−0.0480 (5)	0.06354 (14)	0.1288 (18)
H9	0.6340	0.0161	0.0476	0.155*
C8	0.9082 (10)	−0.0374 (7)	0.03860 (16)	0.140 (2)
H8A	0.9932	−0.1035	0.0532	0.168*
H8B	0.8942	−0.0616	0.0046	0.168*
C14	1.0115 (8)	0.4096 (5)	0.07156 (16)	0.140 (2)
H14A	1.0309	0.3936	0.0375	0.210*
H14B	1.0641	0.4978	0.0804	0.210*
H14C	0.8805	0.4100	0.0783	0.210*
C13	1.3143 (7)	0.2870 (7)	0.08997 (15)	0.160 (2)
H13A	1.3696	0.2151	0.1093	0.241*
H13B	1.3712	0.3746	0.0977	0.241*
H13C	1.3329	0.2667	0.0562	0.241*
C12	0.6404 (13)	−0.1951 (7)	0.06041 (19)	0.217 (4)
H12A	0.6598	−0.2313	0.0283	0.326*
H12B	0.5096	−0.1925	0.0673	0.326*
H12C	0.7017	−0.2537	0.0836	0.326*
C18	0.7548 (7)	0.4780 (4)	0.18901 (13)	0.0971 (12)
H18A	0.6422	0.4507	0.1721	0.117*
H18B	0.8618	0.4566	0.1689	0.117*
C15	0.7871 (6)	0.5142 (4)	0.27610 (13)	0.0967 (13)
H15A	0.6884	0.5045	0.2999	0.116*
H15B	0.9064	0.5059	0.2923	0.116*
C17	0.7505 (7)	0.6280 (4)	0.20278 (19)	0.1103 (14)
H17	0.7344	0.7001	0.1807	0.132*
C16	0.7720 (7)	0.6461 (5)	0.2495 (2)	0.1092 (14)
H16	0.7772	0.7329	0.2643	0.131*
N1	0.7681 (5)	0.4111 (3)	0.23671 (9)	0.0791 (9)
O3	0.8607 (3)	0.1789 (2)	0.17127 (7)	0.0767 (7)
O1	0.6832 (4)	0.0450 (2)	0.22383 (8)	0.0845 (8)
O2	0.6958 (5)	−0.0440 (3)	0.29863 (9)	0.1111 (10)

	U11	U22	U33	U12	U13	U23
Cl1	0.1428 (11)	0.1448 (9)	0.0630 (6)	0.0000 (9)	−0.0027 (6)	−0.0123 (6)
C3	0.057 (2)	0.086 (2)	0.065 (2)	0.002 (2)	0.0010 (19)	−0.009 (2)
C4	0.067 (3)	0.089 (3)	0.068 (2)	0.002 (2)	0.002 (2)	−0.0044 (19)
C5	0.084 (3)	0.096 (3)	0.053 (2)	0.012 (2)	−0.0074 (19)	−0.0018 (17)
C1	0.082 (3)	0.096 (3)	0.074 (3)	0.008 (3)	0.009 (2)	0.003 (2)
C2	0.072 (3)	0.100 (3)	0.061 (2)	0.005 (2)	0.001 (2)	−0.0071 (19)
C6	0.082 (3)	0.132 (4)	0.056 (2)	0.024 (3)	0.001 (2)	0.000 (2)
C10	0.131 (4)	0.107 (3)	0.066 (2)	−0.005 (3)	−0.007 (3)	−0.0180 (19)
C7	0.144 (5)	0.155 (5)	0.057 (2)	0.018 (4)	0.007 (3)	−0.011 (3)
C11	0.093 (4)	0.161 (5)	0.060 (2)	−0.010 (3)	0.009 (2)	−0.007 (3)
C9	0.182 (6)	0.129 (4)	0.075 (3)	−0.010 (4)	−0.010 (4)	−0.028 (3)
C8	0.193 (7)	0.155 (5)	0.071 (3)	0.011 (5)	0.012 (3)	−0.038 (3)
C14	0.165 (6)	0.146 (4)	0.110 (3)	−0.015 (4)	0.009 (4)	0.025 (3)
C13	0.098 (4)	0.294 (8)	0.088 (3)	−0.019 (5)	0.027 (3)	−0.011 (4)
C12	0.325 (10)	0.197 (6)	0.130 (4)	−0.106 (7)	0.031 (5)	−0.073 (4)
C18	0.097 (3)	0.098 (3)	0.097 (3)	0.007 (3)	0.010 (3)	0.010 (2)
C15	0.082 (3)	0.101 (3)	0.107 (3)	−0.010 (3)	−0.002 (3)	−0.022 (3)
C17	0.106 (4)	0.085 (3)	0.141 (4)	0.004 (3)	0.015 (4)	0.016 (3)
C16	0.088 (3)	0.088 (3)	0.152 (4)	−0.009 (3)	0.003 (3)	−0.021 (3)
N1	0.081 (3)	0.088 (2)	0.0686 (17)	0.0027 (19)	0.0051 (18)	−0.0100 (16)
O3	0.0764 (17)	0.1003 (17)	0.0532 (13)	0.0049 (14)	0.0025 (13)	−0.0071 (12)
O1	0.097 (2)	0.0833 (17)	0.0735 (15)	−0.0071 (15)	0.0035 (14)	−0.0038 (13)
O2	0.136 (3)	0.103 (2)	0.0939 (18)	0.016 (2)	0.0152 (19)	0.0119 (16)

Cl1—C2	1.709 (3)	C9—C8	1.518 (7)
C3—N1	1.321 (4)	C9—C12	1.530 (7)
C3—C2	1.347 (4)	C9—H9	0.9800
C3—C4	1.512 (4)	C8—H8A	0.9700
C4—O3	1.393 (4)	C8—H8B	0.9700
C4—O1	1.441 (4)	C14—H14A	0.9600
C4—H4	0.9800	C14—H14B	0.9600
C5—O3	1.453 (3)	C14—H14C	0.9600
C5—C10	1.507 (5)	C13—H13A	0.9600
C5—C6	1.536 (5)	C13—H13B	0.9600
C5—H5	0.9800	C13—H13C	0.9600
C1—O2	1.206 (4)	C12—H12A	0.9600
C1—O1	1.375 (4)	C12—H12B	0.9600
C1—C2	1.418 (5)	C12—H12C	0.9600
C6—C11	1.522 (6)	C18—N1	1.466 (4)
C6—C7	1.535 (5)	C18—C17	1.492 (5)
C6—H6	0.9800	C18—H18A	0.9700
C10—C9	1.542 (5)	C18—H18B	0.9700
C10—H10A	0.9700	C15—C16	1.469 (6)
C10—H10B	0.9700	C15—N1	1.476 (4)
C7—C8	1.504 (6)	C15—H15A	0.9700
C7—H7A	0.9700	C15—H15B	0.9700
C7—H7B	0.9700	C17—C16	1.308 (5)
C11—C14	1.524 (6)	C17—H17	0.9300
C11—C13	1.535 (6)	C16—H16	0.9300
C11—H11	0.9800
N1—C3—C2	133.1 (3)	C12—C9—H9	108.6
N1—C3—C4	119.9 (3)	C10—C9—H9	108.6
C2—C3—C4	107.0 (3)	C7—C8—C9	112.1 (5)
O3—C4—O1	109.9 (3)	C7—C8—H8A	109.2
O3—C4—C3	109.8 (3)	C9—C8—H8A	109.2
O1—C4—C3	105.0 (3)	C7—C8—H8B	109.2
O3—C4—H4	110.7	C9—C8—H8B	109.2
O1—C4—H4	110.7	H8A—C8—H8B	107.9
C3—C4—H4	110.7	C11—C14—H14A	109.5
O3—C5—C10	112.2 (3)	C11—C14—H14B	109.5
O3—C5—C6	105.0 (3)	H14A—C14—H14B	109.5
C10—C5—C6	112.8 (4)	C11—C14—H14C	109.5
O3—C5—H5	108.9	H14A—C14—H14C	109.5
C10—C5—H5	108.9	H14B—C14—H14C	109.5
C6—C5—H5	108.9	C11—C13—H13A	109.5
O2—C1—O1	119.6 (4)	C11—C13—H13B	109.5
O2—C1—C2	130.8 (3)	H13A—C13—H13B	109.5
O1—C1—C2	109.6 (3)	C11—C13—H13C	109.5
C3—C2—C1	110.1 (3)	H13A—C13—H13C	109.5
C3—C2—Cl1	130.7 (3)	H13B—C13—H13C	109.5
C1—C2—Cl1	119.2 (3)	C9—C12—H12A	109.5
C11—C6—C7	113.7 (4)	C9—C12—H12B	109.5
C11—C6—C5	114.4 (3)	H12A—C12—H12B	109.5
C7—C6—C5	108.6 (4)	C9—C12—H12C	109.5
C11—C6—H6	106.5	H12A—C12—H12C	109.5
C7—C6—H6	106.5	H12B—C12—H12C	109.5
C5—C6—H6	106.5	N1—C18—C17	101.4 (3)
C5—C10—C9	111.4 (3)	N1—C18—H18A	111.5
C5—C10—H10A	109.3	C17—C18—H18A	111.5
C9—C10—H10A	109.3	N1—C18—H18B	111.5
C5—C10—H10B	109.3	C17—C18—H18B	111.5
C9—C10—H10B	109.3	H18A—C18—H18B	109.3
H10A—C10—H10B	108.0	C16—C15—N1	102.0 (3)
C8—C7—C6	112.2 (4)	C16—C15—H15A	111.4
C8—C7—H7A	109.2	N1—C15—H15A	111.4
C6—C7—H7A	109.2	C16—C15—H15B	111.4
C8—C7—H7B	109.2	N1—C15—H15B	111.4
C6—C7—H7B	109.2	H15A—C15—H15B	109.2
H7A—C7—H7B	107.9	C16—C17—C18	112.1 (4)
C6—C11—C14	114.0 (4)	C16—C17—H17	123.9
C6—C11—C13	111.5 (5)	C18—C17—H17	123.9
C14—C11—C13	111.4 (5)	C17—C16—C15	112.5 (4)
C6—C11—H11	106.5	C17—C16—H16	123.7
C14—C11—H11	106.5	C15—C16—H16	123.7
C13—C11—H11	106.5	C3—N1—C18	124.5 (3)
C8—C9—C12	111.8 (5)	C3—N1—C15	123.3 (3)
C8—C9—C10	108.9 (4)	C18—N1—C15	111.7 (3)
C12—C9—C10	110.4 (4)	C4—O3—C5	116.2 (3)
C8—C9—H9	108.6	C1—O1—C4	108.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C16—H16···O2i	0.93	2.42	3.320 (6)	164

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C16—H16⋯O2i	0.93	2.42	3.320 (6)	164

Symmetry code: (i) .