(S)-3-Bromo-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)BrNO(3), was obtained via a tandem asymmetric Michael addition-elimination reaction of 3,4-dibromo-5-(S)-(l-menth-yloxy)-2(5H)-furan-one and diallyl-amine in the presence of potassium fluoride. In the mol-ecule, the five-membered furan-one ring is approximately planar [maximum atomic deviation = 0.030 (3) Å], and the six-membered cyclo-hexane ring adopts a chair conformation.

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: Gondela & Walczak (2010 ▶); Tanoury et al. (2008 ▶); Kimura et al. (2000 ▶). For asymmetric Michael addition reactions of 2(5H)-furan­one, see: Hoffmann et al. (2006 ▶); He et al. (2006) ▶. For the synthesis of the title compound, see: Song et al. (2009 ▶).

Experimental

Crystal data

C20H30BrNO3

M = 412.35

Orthorhombic,

a = 8.5215 (16) Å

b = 11.934 (2) Å

c = 20.603 (4) Å

V = 2095.2 (7) Å3

Z = 4

Mo Kα radiation

μ = 1.98 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 = 0.641, T max = 0.729

19608 measured reflections

3640 independent reflections

2660 reflections with I > 2σ(I)

R int = 0.078

Refinement

R[F 2 > 2σ(F 2)] = 0.037

wR(F 2) = 0.075

S = 1.04

3640 reflections

230 parameters

H-atom parameters constrained

Δρmax = 0.28 e Å−3

Δρmin = −0.21 e Å−3

Absolute structure: Flack (1983 ▶), 1543 Friedel pairs

Flack parameter: 0.001 (9)

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/S1600536810047173/xu5089sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810047173/xu5089Isup2.hkl

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

C20H30BrNO3	F(000) = 864
Mr = 412.35	Dx = 1.307 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 3500 reflections
a = 8.5215 (16) Å	θ = 2.6–20.9°
b = 11.934 (2) Å	µ = 1.98 mm−1
c = 20.603 (4) Å	T = 298 K
V = 2095.2 (7) Å3	Block, colourless
Z = 4	0.23 × 0.20 × 0.16 mm

Bruker APEXII area-detector diffractometer	3640 independent reflections
Radiation source: fine-focus sealed tube	2660 reflections with I > 2σ(I)
graphite	Rint = 0.078
φ and ω scan	θmax = 24.9°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
Tmin = 0.641, Tmax = 0.729	k = −14→14
19608 measured reflections	l = −24→24

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)] = 0.037	H-atom parameters constrained
wR(F2) = 0.075	w = 1/[σ2(Fo2) + (0.P)2 + 0.1072P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max < 0.001
3640 reflections	Δρmax = 0.28 e Å−3
230 parameters	Δρmin = −0.21 e Å−3
0 restraints	Absolute structure: Flack (1983), 1543 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.001 (9)

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
Br1	0.27706 (5)	−0.04364 (3)	0.92085 (2)	0.07258 (18)
O3	0.2972 (3)	0.36270 (16)	0.96994 (9)	0.0435 (5)
O2	0.3680 (3)	0.21670 (19)	1.03849 (10)	0.0574 (7)
O1	0.2726 (3)	0.0470 (2)	1.06339 (12)	0.0797 (8)
C4	0.2198 (4)	0.5548 (3)	0.97362 (17)	0.0567 (9)
H4	0.1129	0.5295	0.9834	0.068*
C9	0.3298 (4)	0.4689 (3)	1.00221 (16)	0.0479 (9)
H9	0.4381	0.4911	0.9927	0.057*
C8	0.3107 (4)	0.4579 (3)	1.07491 (17)	0.0579 (8)
H8A	0.3878	0.4051	1.0911	0.070*
H8B	0.2074	0.4277	1.0842	0.070*
C6	0.2203 (5)	0.6563 (3)	1.0818 (2)	0.0822 (12)
H6A	0.1126	0.6350	1.0907	0.099*
H6B	0.2394	0.7284	1.1021	0.099*
C3	0.2302 (4)	0.5667 (3)	0.89958 (18)	0.0670 (11)
H3	0.2262	0.4906	0.8819	0.080*
C5	0.2427 (5)	0.6670 (3)	1.0096 (2)	0.0798 (13)
H5A	0.3476	0.6949	1.0010	0.096*
H5B	0.1685	0.7214	0.9928	0.096*
C2	0.3854 (5)	0.6182 (4)	0.8759 (2)	0.0923 (14)
H2A	0.3909	0.6952	0.8892	0.138*
H2B	0.3903	0.6140	0.8294	0.138*
H2C	0.4719	0.5776	0.8943	0.138*
C10	0.3028 (6)	0.5538 (4)	1.1835 (2)	0.1184 (18)
H10A	0.1984	0.5261	1.1906	0.178*
H10B	0.3154	0.6243	1.2054	0.178*
H10C	0.3774	0.5009	1.2003	0.178*
C7	0.3301 (4)	0.5697 (3)	1.1109 (2)	0.0727 (12)
H7	0.4382	0.5956	1.1046	0.087*
C12	0.3881 (3)	0.1916 (2)	0.92585 (17)	0.0411 (7)
C11	0.4052 (4)	0.2769 (3)	0.98021 (15)	0.0441 (8)
H11	0.5124	0.3065	0.9819	0.053*
C13	0.3321 (4)	0.0962 (3)	0.95381 (17)	0.0468 (9)
C14	0.3192 (4)	0.1112 (3)	1.02266 (19)	0.0557 (10)
N1	0.4230 (3)	0.2185 (2)	0.86442 (14)	0.0512 (8)
C16	0.6441 (5)	0.3143 (3)	0.81261 (19)	0.0658 (11)
H16	0.7254	0.2830	0.8366	0.079*
C17	0.6743 (6)	0.3435 (3)	0.7539 (2)	0.0898 (14)
H17A	0.5960	0.3751	0.7283	0.108*
H17B	0.7744	0.3329	0.7369	0.108*
C15	0.4897 (4)	0.3267 (3)	0.84513 (18)	0.0547 (10)
H15A	0.5020	0.3734	0.8833	0.066*
H15B	0.4175	0.3642	0.8159	0.066*
C18	0.3789 (5)	0.1460 (3)	0.81058 (17)	0.0659 (11)
H18A	0.3965	0.0687	0.8231	0.079*
H18B	0.4467	0.1620	0.7739	0.079*
C19	0.2127 (6)	0.1588 (4)	0.7897 (2)	0.0828 (13)
H19	0.1814	0.1184	0.7534	0.099*
C20	0.1081 (6)	0.2206 (4)	0.8173 (2)	0.0991 (16)
H20A	0.1340	0.2626	0.8538	0.119*
H20B	0.0067	0.2232	0.8006	0.119*
C1	0.0902 (5)	0.6287 (4)	0.8715 (2)	0.0987 (16)
H1A	0.0917	0.7051	0.8861	0.148*
H1B	−0.0049	0.5934	0.8857	0.148*
H1C	0.0954	0.6269	0.8250	0.148*

	U11	U22	U33	U12	U13	U23
Br1	0.0696 (3)	0.0426 (2)	0.1055 (3)	−0.0069 (2)	0.0069 (2)	−0.0098 (2)
O3	0.0464 (13)	0.0334 (11)	0.0508 (13)	0.0051 (11)	0.0006 (11)	−0.0065 (10)
O2	0.0797 (18)	0.0465 (14)	0.0460 (15)	0.0092 (13)	0.0040 (13)	0.0029 (12)
O1	0.1046 (19)	0.0580 (15)	0.0766 (18)	0.0109 (18)	0.0256 (16)	0.0173 (14)
C4	0.050 (2)	0.0383 (18)	0.082 (3)	−0.001 (2)	0.008 (2)	−0.0055 (17)
C9	0.0412 (19)	0.0343 (18)	0.068 (3)	−0.0073 (16)	0.0054 (16)	−0.0098 (17)
C8	0.055 (2)	0.054 (2)	0.065 (2)	0.0018 (19)	0.002 (2)	−0.011 (2)
C6	0.071 (3)	0.054 (2)	0.122 (4)	−0.005 (2)	0.011 (3)	−0.039 (2)
C3	0.071 (3)	0.046 (2)	0.084 (3)	0.004 (2)	0.012 (2)	0.0154 (17)
C5	0.073 (3)	0.040 (2)	0.126 (4)	0.000 (2)	0.007 (3)	−0.012 (2)
C2	0.094 (4)	0.068 (3)	0.115 (4)	0.001 (3)	0.031 (3)	0.028 (3)
C10	0.141 (4)	0.129 (4)	0.085 (4)	0.017 (4)	0.002 (3)	−0.060 (3)
C7	0.057 (2)	0.071 (3)	0.090 (3)	−0.001 (2)	0.007 (2)	−0.039 (2)
C12	0.0338 (17)	0.0386 (18)	0.051 (2)	0.0041 (13)	0.0021 (18)	−0.0023 (18)
C11	0.046 (2)	0.0382 (18)	0.048 (2)	0.0053 (16)	0.0020 (17)	−0.0017 (17)
C13	0.048 (2)	0.0388 (19)	0.053 (2)	0.0103 (16)	0.0032 (17)	−0.0003 (16)
C14	0.055 (3)	0.039 (2)	0.073 (3)	0.0175 (18)	0.015 (2)	0.0080 (19)
N1	0.0573 (19)	0.0478 (17)	0.048 (2)	−0.0038 (15)	0.0100 (15)	−0.0076 (15)
C16	0.070 (3)	0.067 (3)	0.061 (3)	−0.006 (2)	0.006 (2)	0.009 (2)
C17	0.107 (4)	0.082 (3)	0.081 (3)	0.005 (3)	0.018 (3)	0.021 (2)
C15	0.065 (3)	0.046 (2)	0.054 (2)	−0.0049 (18)	0.007 (2)	−0.0010 (17)
C18	0.084 (3)	0.064 (3)	0.050 (2)	−0.014 (2)	0.010 (2)	−0.015 (2)
C19	0.086 (3)	0.097 (3)	0.065 (3)	−0.024 (3)	−0.017 (3)	0.003 (2)
C20	0.070 (3)	0.125 (4)	0.103 (4)	−0.011 (3)	−0.018 (3)	0.037 (4)
C1	0.099 (4)	0.086 (3)	0.111 (4)	0.017 (3)	0.003 (3)	0.030 (3)

Br1—C13	1.862 (3)	C10—H10A	0.9600
O3—C11	1.393 (4)	C10—H10B	0.9600
O3—C9	1.458 (3)	C10—H10C	0.9600
O2—C14	1.365 (4)	C7—H7	0.9800
O2—C11	1.434 (4)	C12—N1	1.339 (4)
O1—C14	1.204 (4)	C12—C13	1.362 (4)
C4—C9	1.509 (4)	C12—C11	1.521 (4)
C4—C3	1.535 (5)	C11—H11	0.9800
C4—C5	1.542 (4)	C13—C14	1.434 (5)
C4—H4	0.9800	N1—C18	1.456 (4)
C9—C8	1.512 (4)	N1—C15	1.466 (4)
C9—H9	0.9800	C16—C17	1.285 (5)
C8—C7	1.535 (5)	C16—C15	1.484 (5)
C8—H8A	0.9700	C16—H16	0.9300
C8—H8B	0.9700	C17—H17A	0.9300
C6—C5	1.505 (5)	C17—H17B	0.9300
C6—C7	1.518 (5)	C15—H15A	0.9700
C6—H6A	0.9700	C15—H15B	0.9700
C6—H6B	0.9700	C18—C19	1.488 (6)
C3—C1	1.518 (5)	C18—H18A	0.9700
C3—C2	1.538 (5)	C18—H18B	0.9700
C3—H3	0.9800	C19—C20	1.288 (6)
C5—H5A	0.9700	C19—H19	0.9300
C5—H5B	0.9700	C20—H20A	0.9300
C2—H2A	0.9600	C20—H20B	0.9300
C2—H2B	0.9600	C1—H1A	0.9600
C2—H2C	0.9600	C1—H1B	0.9600
C10—C7	1.526 (6)	C1—H1C	0.9600
C11—O3—C9	116.3 (2)	C10—C7—C8	110.4 (3)
C14—O2—C11	109.2 (3)	C6—C7—H7	108.2
C9—C4—C3	114.5 (3)	C10—C7—H7	108.2
C9—C4—C5	108.9 (3)	C8—C7—H7	108.2
C3—C4—C5	112.9 (3)	N1—C12—C13	132.7 (3)
C9—C4—H4	106.7	N1—C12—C11	120.9 (3)
C3—C4—H4	106.7	C13—C12—C11	106.3 (3)
C5—C4—H4	106.7	O3—C11—O2	110.5 (3)
O3—C9—C4	107.1 (2)	O3—C11—C12	108.5 (2)
O3—C9—C8	110.9 (3)	O2—C11—C12	105.1 (2)
C4—C9—C8	112.3 (3)	O3—C11—H11	110.9
O3—C9—H9	108.8	O2—C11—H11	110.9
C4—C9—H9	108.8	C12—C11—H11	110.9
C8—C9—H9	108.8	C12—C13—C14	109.9 (3)
C9—C8—C7	113.1 (3)	C12—C13—Br1	133.1 (3)
C9—C8—H8A	109.0	C14—C13—Br1	117.0 (2)
C7—C8—H8A	109.0	O1—C14—O2	121.4 (3)
C9—C8—H8B	109.0	O1—C14—C13	129.4 (3)
C7—C8—H8B	109.0	O2—C14—C13	109.2 (3)
H8A—C8—H8B	107.8	C12—N1—C18	121.3 (3)
C5—C6—C7	111.8 (3)	C12—N1—C15	123.6 (3)
C5—C6—H6A	109.3	C18—N1—C15	114.7 (3)
C7—C6—H6A	109.3	C17—C16—C15	125.1 (4)
C5—C6—H6B	109.3	C17—C16—H16	117.4
C7—C6—H6B	109.3	C15—C16—H16	117.4
H6A—C6—H6B	107.9	C16—C17—H17A	120.0
C1—C3—C4	112.2 (3)	C16—C17—H17B	120.0
C1—C3—C2	111.1 (3)	H17A—C17—H17B	120.0
C4—C3—C2	113.7 (3)	N1—C15—C16	112.2 (3)
C1—C3—H3	106.4	N1—C15—H15A	109.2
C4—C3—H3	106.4	C16—C15—H15A	109.2
C2—C3—H3	106.4	N1—C15—H15B	109.2
C6—C5—C4	112.7 (3)	C16—C15—H15B	109.2
C6—C5—H5A	109.1	H15A—C15—H15B	107.9
C4—C5—H5A	109.1	N1—C18—C19	113.9 (4)
C6—C5—H5B	109.1	N1—C18—H18A	108.8
C4—C5—H5B	109.1	C19—C18—H18A	108.8
H5A—C5—H5B	107.8	N1—C18—H18B	108.8
C3—C2—H2A	109.5	C19—C18—H18B	108.8
C3—C2—H2B	109.5	H18A—C18—H18B	107.7
H2A—C2—H2B	109.5	C20—C19—C18	126.2 (5)
C3—C2—H2C	109.5	C20—C19—H19	116.9
H2A—C2—H2C	109.5	C18—C19—H19	116.9
H2B—C2—H2C	109.5	C19—C20—H20A	120.0
C7—C10—H10A	109.5	C19—C20—H20B	120.0
C7—C10—H10B	109.5	H20A—C20—H20B	120.0
H10A—C10—H10B	109.5	C3—C1—H1A	109.5
C7—C10—H10C	109.5	C3—C1—H1B	109.5
H10A—C10—H10C	109.5	H1A—C1—H1B	109.5
H10B—C10—H10C	109.5	C3—C1—H1C	109.5
C6—C7—C10	112.2 (3)	H1A—C1—H1C	109.5
C6—C7—C8	109.5 (3)	H1B—C1—H1C	109.5
C11—O3—C9—C4	168.3 (2)	C13—C12—C11—O3	−113.1 (3)
C11—O3—C9—C8	−68.9 (3)	N1—C12—C11—O2	−176.3 (3)
C3—C4—C9—O3	−56.2 (3)	C13—C12—C11—O2	5.0 (3)
C5—C4—C9—O3	176.3 (3)	N1—C12—C13—C14	178.5 (3)
C3—C4—C9—C8	−178.1 (3)	C11—C12—C13—C14	−3.0 (4)
C5—C4—C9—C8	54.4 (4)	N1—C12—C13—Br1	0.3 (6)
O3—C9—C8—C7	−175.2 (3)	C11—C12—C13—Br1	178.8 (3)
C4—C9—C8—C7	−55.4 (4)	C11—O2—C14—O1	−175.5 (3)
C9—C4—C3—C1	164.3 (3)	C11—O2—C14—C13	3.6 (4)
C5—C4—C3—C1	−70.3 (4)	C12—C13—C14—O1	178.8 (3)
C9—C4—C3—C2	−68.5 (4)	Br1—C13—C14—O1	−2.6 (5)
C5—C4—C3—C2	56.9 (4)	C12—C13—C14—O2	−0.2 (4)
C7—C6—C5—C4	57.1 (4)	Br1—C13—C14—O2	178.3 (2)
C9—C4—C5—C6	−55.9 (4)	C13—C12—N1—C18	10.4 (5)
C3—C4—C5—C6	175.7 (3)	C11—C12—N1—C18	−167.9 (3)
C5—C6—C7—C10	−177.1 (3)	C13—C12—N1—C15	−177.2 (3)
C5—C6—C7—C8	−54.0 (4)	C11—C12—N1—C15	4.5 (5)
C9—C8—C7—C6	53.5 (4)	C12—N1—C15—C16	120.4 (3)
C9—C8—C7—C10	177.6 (3)	C18—N1—C15—C16	−66.7 (4)
C9—O3—C11—O2	85.9 (3)	C17—C16—C15—N1	117.8 (4)
C9—O3—C11—C12	−159.4 (2)	C12—N1—C18—C19	80.9 (4)
C14—O2—C11—O3	111.6 (3)	C15—N1—C18—C19	−92.2 (4)
C14—O2—C11—C12	−5.2 (3)	N1—C18—C19—C20	−4.7 (7)
N1—C12—C11—O3	65.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
C20—H20A···N1	0.93	2.53	2.854 (6)	101
C18—H18A···Br1	0.97	2.62	3.322 (4)	129
C15—H15A···O3	0.97	2.50	3.081 (4)	118
C8—H8A···O2	0.97	2.50	3.015 (4)	113
C3—H3···O3	0.98	2.45	2.891 (4)	107