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

The title compound, C(20)H(30)ClNO(3), was obtained via a tandem asymmetric Michael addition-elimination reaction of (5S)-3,4-dichloro-5-(l-menth-yloxy)-2(5H)-furan-one and diallyl-amine in the presence of potassium fluoride. The mol-ecular structure contains an approximately planar five-membered furan-one ring [maximum atomic deviation = 0.0221 (3) Å] and a six-membered ring adopting a chair conformation.

Related literature

For the biological activity of 4-amino-2(5H)-furan­ones, see: Gondela & Walczak (2010 ▶). For chemical, pharmaceutical and agrochemical applications of 3,4-amino-2(5H)-furan­ones, see: Tanoury et al. (2008 ▶); Kimura et al. (2000 ▶). For the synthesis of optically pure 5-(l-menth­yloxy)-3,4-dichloro-2(5H)-furan­ones, see: Song et al. (2009 ▶). For the use of inter­mediate chiral 5-S-(l-menth­yloxy)-2(5H)-furan­ones, see: Hoffmann et al. (2006 ▶).

Experimental

Crystal data

C20H30ClNO3

M = 367.90

Orthorhombic,

a = 8.4540 (17) Å

b = 11.722 (2) Å

c = 20.648 (4) Å

V = 2046.1 (7) Å3

Z = 4

Mo Kα radiation

μ = 0.20 mm−1

T = 273 K

0.23 × 0.20 × 0.16 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.954, T max = 0.968

9931 measured reflections

3950 independent reflections

2923 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.102

S = 0.97

3950 reflections

230 parameters

H-atom parameters constrained

Δρmax = 0.11 e Å−3

Δρmin = −0.13 e Å−3

Absolute structure: Flack (1983 ▶), 1677 Friedel pairs

Flack parameter: −0.06 (6)

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 datablock(s) global, I. DOI: 10.1107/S1600536811027772/zq2113sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811027772/zq2113Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811027772/zq2113Isup3.cml

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

C20H30ClNO3	F(000) = 792.0
Mr = 367.90	Dx = 1.194 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2994 reflections
a = 8.4540 (17) Å	θ = 2.6–22.1°
b = 11.722 (2) Å	µ = 0.20 mm−1
c = 20.648 (4) Å	T = 273 K
V = 2046.1 (7) Å3	Block, colourless
Z = 4	0.23 × 0.20 × 0.16 mm

Bruker APEXII CCD area-detector diffractometer	3950 independent reflections
Radiation source: fine-focus sealed tube	2923 reflections with I > 2σ(I)
graphite	Rint = 0.033
phi and ω scans	θmax = 26.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→8
Tmin = 0.954, Tmax = 0.968	k = −14→14
9931 measured reflections	l = −22→25

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.038	w = 1/[σ2(Fo2) + (0.0584P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.102	(Δ/σ)max < 0.001
S = 0.97	Δρmax = 0.11 e Å−3
3950 reflections	Δρmin = −0.13 e Å−3
230 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.0125 (18)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1677 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: −0.06 (6)

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
Cl1	0.27814 (9)	0.46092 (4)	0.91712 (3)	0.0767 (2)
C14	0.3852 (2)	0.68664 (15)	0.92440 (10)	0.0450 (5)
C12	0.3084 (3)	0.60235 (16)	1.01887 (11)	0.0553 (5)
C13	0.3270 (3)	0.58965 (15)	0.95061 (10)	0.0513 (5)
C11	0.3995 (3)	0.77169 (15)	0.97949 (9)	0.0455 (5)
H11	0.5078	0.8009	0.9827	0.055*
C4	0.2172 (3)	1.05546 (15)	0.97288 (11)	0.0560 (5)
H4	0.1096	1.0295	0.9827	0.067*
C8	0.3116 (3)	0.95600 (17)	1.07345 (10)	0.0595 (6)
H8A	0.3896	0.9024	1.0895	0.071*
H8B	0.2077	0.9252	1.0830	0.071*
C9	0.3297 (3)	0.96703 (16)	1.00113 (9)	0.0496 (5)
H9	0.4389	0.9890	0.9911	0.060*
C6	0.2206 (4)	1.1564 (2)	1.08117 (14)	0.0844 (8)
H6A	0.2396	1.2296	1.1017	0.101*
H6B	0.1125	1.1341	1.0905	0.101*
C19	0.6469 (3)	0.81529 (18)	0.81335 (11)	0.0645 (6)
H19	0.7300	0.7852	0.8374	0.077*
C5	0.2408 (4)	1.16881 (17)	1.00889 (14)	0.0805 (8)
H5A	0.3461	1.1976	0.9999	0.097*
H5B	0.1652	1.2242	0.9928	0.097*
C18	0.4919 (3)	0.82587 (17)	0.84594 (11)	0.0591 (6)
H18A	0.5042	0.8718	0.8847	0.071*
H18B	0.4189	0.8652	0.8174	0.071*
C20	0.6762 (4)	0.8440 (2)	0.75483 (13)	0.0879 (9)
H20A	0.5963	0.8744	0.7291	0.105*
H20B	0.7774	0.8345	0.7380	0.105*
C15	0.3794 (3)	0.6432 (2)	0.80906 (11)	0.0696 (7)
H15A	0.3966	0.5640	0.8207	0.083*
H15B	0.4479	0.6606	0.7727	0.083*
C3	0.2284 (3)	1.06627 (18)	0.89904 (12)	0.0692 (7)
H3	0.2244	0.9886	0.8815	0.083*
C2	0.0861 (4)	1.1300 (3)	0.87141 (16)	0.1021 (11)
H2A	0.0887	1.1263	0.8250	0.153*
H2B	0.0897	1.2083	0.8850	0.153*
H2C	−0.0096	1.0954	0.8869	0.153*
C7	0.3313 (3)	1.0696 (2)	1.10909 (12)	0.0737 (8)
H7	0.4397	1.0964	1.1019	0.088*
C17	0.1074 (4)	0.7219 (3)	0.81581 (15)	0.0960 (10)
H17A	0.1338	0.7650	0.8521	0.115*
H17B	0.0053	0.7251	0.7991	0.115*
C16	0.2130 (5)	0.6574 (3)	0.78848 (13)	0.0877 (9)
H16	0.1808	0.6161	0.7524	0.105*
C1	0.3837 (4)	1.1195 (3)	0.87538 (15)	0.0915 (9)
H1A	0.4714	1.0808	0.8952	0.137*
H1B	0.3862	1.1988	0.8870	0.137*
H1C	0.3908	1.1121	0.8292	0.137*
C10	0.3083 (5)	1.0534 (3)	1.18160 (13)	0.1167 (12)
H10A	0.2053	1.0221	1.1896	0.175*
H10B	0.3177	1.1258	1.2030	0.175*
H10C	0.3876	1.0023	1.1979	0.175*
O1	0.29340 (17)	0.86000 (10)	0.96896 (6)	0.0459 (3)
O3	0.2592 (2)	0.53592 (13)	1.05869 (8)	0.0787 (5)
O2	0.3578 (2)	0.70923 (11)	1.03625 (6)	0.0578 (4)
N1	0.4245 (2)	0.71508 (14)	0.86380 (8)	0.0535 (5)

	U11	U22	U33	U12	U13	U23
Cl1	0.0780 (5)	0.0447 (3)	0.1075 (5)	−0.0086 (3)	0.0051 (4)	−0.0110 (3)
C14	0.0359 (12)	0.0431 (10)	0.0560 (12)	0.0047 (8)	0.0009 (10)	−0.0023 (9)
C12	0.0476 (14)	0.0461 (11)	0.0721 (14)	0.0114 (10)	0.0083 (12)	0.0082 (10)
C13	0.0499 (14)	0.0391 (10)	0.0650 (13)	0.0052 (9)	0.0028 (11)	−0.0034 (9)
C11	0.0420 (13)	0.0424 (10)	0.0520 (11)	0.0048 (8)	0.0026 (10)	0.0002 (9)
C4	0.0468 (13)	0.0410 (10)	0.0802 (14)	0.0021 (9)	0.0065 (12)	0.0006 (9)
C8	0.0590 (15)	0.0544 (12)	0.0651 (13)	0.0027 (11)	0.0038 (12)	−0.0137 (10)
C9	0.0429 (12)	0.0384 (9)	0.0676 (13)	−0.0027 (9)	0.0066 (10)	−0.0081 (9)
C6	0.0707 (19)	0.0605 (13)	0.122 (2)	0.0036 (13)	0.0113 (19)	−0.0395 (14)
C19	0.0649 (17)	0.0676 (14)	0.0611 (14)	−0.0026 (11)	0.0068 (12)	0.0045 (11)
C5	0.0714 (18)	0.0416 (11)	0.128 (2)	0.0022 (11)	0.0092 (18)	−0.0092 (12)
C18	0.0696 (18)	0.0510 (12)	0.0567 (13)	−0.0041 (11)	0.0104 (12)	−0.0008 (9)
C20	0.102 (3)	0.0845 (18)	0.0771 (18)	0.0078 (16)	0.0255 (17)	0.0160 (13)
C15	0.085 (2)	0.0660 (14)	0.0577 (13)	−0.0072 (13)	0.0093 (14)	−0.0186 (11)
C3	0.0683 (18)	0.0532 (12)	0.0860 (17)	0.0052 (11)	0.0083 (14)	0.0154 (11)
C2	0.097 (3)	0.093 (2)	0.117 (2)	0.0256 (18)	−0.001 (2)	0.0334 (19)
C7	0.0587 (18)	0.0717 (15)	0.0907 (18)	−0.0038 (12)	0.0042 (14)	−0.0356 (13)
C17	0.072 (2)	0.112 (2)	0.103 (2)	0.0005 (18)	−0.0199 (19)	0.0284 (19)
C16	0.095 (3)	0.097 (2)	0.0713 (17)	−0.0248 (18)	−0.0220 (18)	0.0032 (14)
C1	0.091 (2)	0.0711 (17)	0.112 (2)	0.0002 (15)	0.0313 (18)	0.0273 (16)
C10	0.132 (3)	0.124 (2)	0.095 (2)	0.017 (2)	−0.009 (2)	−0.0571 (18)
O1	0.0451 (9)	0.0361 (6)	0.0566 (8)	0.0029 (6)	−0.0014 (7)	−0.0035 (5)
O3	0.0931 (14)	0.0606 (9)	0.0823 (11)	0.0075 (10)	0.0270 (10)	0.0186 (8)
O2	0.0713 (11)	0.0498 (8)	0.0524 (8)	0.0084 (7)	0.0055 (8)	0.0020 (6)
N1	0.0601 (13)	0.0492 (9)	0.0512 (10)	−0.0060 (8)	0.0077 (9)	−0.0074 (8)

Cl1—C13	1.711 (2)	C5—H5B	0.9700
C14—N1	1.337 (3)	C18—N1	1.466 (3)
C14—C13	1.352 (3)	C18—H18A	0.9700
C14—C11	1.517 (3)	C18—H18B	0.9700
C12—O3	1.206 (2)	C20—H20A	0.9300
C12—O2	1.369 (2)	C20—H20B	0.9300
C12—C13	1.426 (3)	C15—N1	1.460 (3)
C11—O1	1.387 (2)	C15—C16	1.479 (4)
C11—O2	1.426 (2)	C15—H15A	0.9700
C11—H11	0.9800	C15—H15B	0.9700
C4—C9	1.523 (3)	C3—C2	1.526 (4)
C4—C3	1.533 (3)	C3—C1	1.534 (4)
C4—C5	1.536 (3)	C3—H3	0.9800
C4—H4	0.9800	C2—H2A	0.9600
C8—C9	1.507 (3)	C2—H2B	0.9600
C8—C7	1.530 (3)	C2—H2C	0.9600
C8—H8A	0.9700	C7—C10	1.521 (4)
C8—H8B	0.9700	C7—H7	0.9800
C9—O1	1.452 (2)	C17—C16	1.299 (4)
C9—H9	0.9800	C17—H17A	0.9300
C6—C7	1.498 (4)	C17—H17B	0.9300
C6—C5	1.509 (4)	C16—H16	0.9300
C6—H6A	0.9700	C1—H1A	0.9600
C6—H6B	0.9700	C1—H1B	0.9600
C19—C20	1.279 (3)	C1—H1C	0.9600
C19—C18	1.478 (4)	C10—H10A	0.9600
C19—H19	0.9300	C10—H10B	0.9600
C5—H5A	0.9700	C10—H10C	0.9600
N1—C14—C13	132.44 (19)	C19—C18—H18B	109.1
N1—C14—C11	121.21 (17)	H18A—C18—H18B	107.8
C13—C14—C11	106.34 (18)	C19—C20—H20A	120.0
O3—C12—O2	121.2 (2)	C19—C20—H20B	120.0
O3—C12—C13	130.1 (2)	H20A—C20—H20B	120.0
O2—C12—C13	108.72 (17)	N1—C15—C16	113.9 (2)
C14—C13—C12	110.37 (18)	N1—C15—H15A	108.8
C14—C13—Cl1	131.91 (17)	C16—C15—H15A	108.8
C12—C13—Cl1	117.71 (15)	N1—C15—H15B	108.8
O1—C11—O2	110.64 (16)	C16—C15—H15B	108.8
O1—C11—C14	108.76 (15)	H15A—C15—H15B	107.7
O2—C11—C14	105.02 (15)	C2—C3—C4	111.3 (2)
O1—C11—H11	110.8	C2—C3—C1	110.9 (2)
O2—C11—H11	110.8	C4—C3—C1	113.8 (2)
C14—C11—H11	110.8	C2—C3—H3	106.8
C9—C4—C3	113.48 (18)	C4—C3—H3	106.8
C9—C4—C5	108.78 (19)	C1—C3—H3	106.8
C3—C4—C5	113.70 (18)	C3—C2—H2A	109.5
C9—C4—H4	106.8	C3—C2—H2B	109.5
C3—C4—H4	106.8	H2A—C2—H2B	109.5
C5—C4—H4	106.8	C3—C2—H2C	109.5
C9—C8—C7	113.01 (18)	H2A—C2—H2C	109.5
C9—C8—H8A	109.0	H2B—C2—H2C	109.5
C7—C8—H8A	109.0	C6—C7—C10	112.5 (2)
C9—C8—H8B	109.0	C6—C7—C8	109.8 (2)
C7—C8—H8B	109.0	C10—C7—C8	110.6 (2)
H8A—C8—H8B	107.8	C6—C7—H7	107.9
O1—C9—C8	110.96 (15)	C10—C7—H7	107.9
O1—C9—C4	106.29 (16)	C8—C7—H7	107.9
C8—C9—C4	111.98 (17)	C16—C17—H17A	120.0
O1—C9—H9	109.2	C16—C17—H17B	120.0
C8—C9—H9	109.2	H17A—C17—H17B	120.0
C4—C9—H9	109.2	C17—C16—C15	126.5 (3)
C7—C6—C5	112.0 (2)	C17—C16—H16	116.8
C7—C6—H6A	109.2	C15—C16—H16	116.8
C5—C6—H6A	109.2	C3—C1—H1A	109.5
C7—C6—H6B	109.2	C3—C1—H1B	109.5
C5—C6—H6B	109.2	H1A—C1—H1B	109.5
H6A—C6—H6B	107.9	C3—C1—H1C	109.5
C20—C19—C18	125.4 (3)	H1A—C1—H1C	109.5
C20—C19—H19	117.3	H1B—C1—H1C	109.5
C18—C19—H19	117.3	C7—C10—H10A	109.5
C6—C5—C4	112.37 (19)	C7—C10—H10B	109.5
C6—C5—H5A	109.1	H10A—C10—H10B	109.5
C4—C5—H5A	109.1	C7—C10—H10C	109.5
C6—C5—H5B	109.1	H10A—C10—H10C	109.5
C4—C5—H5B	109.1	H10B—C10—H10C	109.5
H5A—C5—H5B	107.9	C11—O1—C9	115.87 (15)
N1—C18—C19	112.65 (18)	C12—O2—C11	109.26 (15)
N1—C18—H18A	109.1	C14—N1—C15	121.05 (18)
C19—C18—H18A	109.1	C14—N1—C18	123.58 (16)
N1—C18—H18B	109.1	C15—N1—C18	114.71 (17)
N1—C14—C13—C12	178.7 (2)	C9—C4—C3—C1	−69.3 (2)
C11—C14—C13—C12	−2.5 (2)	C5—C4—C3—C1	55.8 (3)
N1—C14—C13—Cl1	−0.1 (4)	C5—C6—C7—C10	−178.1 (2)
C11—C14—C13—Cl1	178.66 (18)	C5—C6—C7—C8	−54.5 (3)
O3—C12—C13—C14	179.4 (2)	C9—C8—C7—C6	54.1 (3)
O2—C12—C13—C14	−0.8 (2)	C9—C8—C7—C10	178.8 (2)
O3—C12—C13—Cl1	−1.6 (3)	N1—C15—C16—C17	−3.2 (4)
O2—C12—C13—Cl1	178.22 (15)	O2—C11—O1—C9	87.69 (19)
N1—C14—C11—O1	65.3 (2)	C14—C11—O1—C9	−157.46 (15)
C13—C14—C11—O1	−113.67 (19)	C8—C9—O1—C11	−68.4 (2)
N1—C14—C11—O2	−176.28 (18)	C4—C9—O1—C11	169.65 (16)
C13—C14—C11—O2	4.8 (2)	O3—C12—O2—C11	−176.1 (2)
C7—C8—C9—O1	−173.88 (18)	C13—C12—O2—C11	4.0 (2)
C7—C8—C9—C4	−55.3 (3)	O1—C11—O2—C12	111.83 (19)
C3—C4—C9—O1	−56.8 (2)	C14—C11—O2—C12	−5.3 (2)
C5—C4—C9—O1	175.58 (18)	C13—C14—N1—C15	12.0 (4)
C3—C4—C9—C8	−178.10 (18)	C11—C14—N1—C15	−166.6 (2)
C5—C4—C9—C8	54.3 (2)	C13—C14—N1—C18	−177.8 (2)
C7—C6—C5—C4	57.3 (3)	C11—C14—N1—C18	3.6 (3)
C9—C4—C5—C6	−55.5 (3)	C16—C15—N1—C14	79.1 (3)
C3—C4—C5—C6	177.0 (2)	C16—C15—N1—C18	−91.9 (3)
C20—C19—C18—N1	115.5 (3)	C19—C18—N1—C14	122.4 (2)
C9—C4—C3—C2	164.5 (2)	C19—C18—N1—C15	−66.8 (3)
C5—C4—C3—C2	−70.4 (3)