(3S*,4S*,E)-tert-Butyl 3,4-dibromo-5-oxo-cyclo-oct-1-ene-carboxyl-ate.

The title compound, C(13)H(18)Br(2)O(3), was prepared by a bromination reaction of (1E,3Z)-methyl 5-oxocyclo-octa-1,3-diene-carboxyl-ate, which was obtained by an ep-oxy-dation reaction of tert-butyl cyclo-oct-1,3-diene-carboxyl-ate. The crystal structure confirms unequivocally the absolute configuration of both chiral centres to be S. In the crystal, C-H⋯O inter-actions link the mol-ecules into chains running along the c axis.

Related literature

For the Michael addition of enanti­omerically pure lithium amides, see: Davies et al. (2005 ▶). For their importance in pharmacology, see: Fülöp et al. (2001 ▶). For the reactivity of the cyclo­octa-1,5-diene in basic medium, see: Huber et al. (1969 ▶, 1970 ▶). For the preparation of analogous unsaturated cyclo­octane esters, see: Garrido et al. (2008 ▶).

Experimental

Crystal data

C13H18Br2O3

M = 382.09

Orthorhombic,

a = 14.0658 (4) Å

b = 9.5990 (3) Å

c = 11.2657 (3) Å

V = 1521.07 (8) Å3

Z = 4

Cu Kα radiation

μ = 6.76 mm−1

T = 298 K

0.24 × 0.14 × 0.10 mm

Data collection

Bruker APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2006 ▶) T min = 0.370, T max = 0.509

10215 measured reflections

2170 independent reflections

2153 reflections with I > 2σ(I)

R int = 0.048

Refinement

R[F 2 > 2σ(F 2)] = 0.029

wR(F 2) = 0.075

S = 1.09

2170 reflections

166 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.32 e Å−3

Δρmin = −0.46 e Å−3

Absolute structure: Flack (1983 ▶), 803 Friedel pairs

Flack parameter: 0.06 (3)

Data collection: APEX2 (Bruker 2006 ▶); cell refinement: SAINT (Bruker 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: SHELXTL (Sheldrick, 2008 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811053852/bt5753sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811053852/bt5753Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811053852/bt5753Isup3.cml

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

C13H18Br2O3	F(000) = 760
Mr = 382.09	Dx = 1.669 Mg m−3
Orthorhombic, Pca21	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2c -2ac	Cell parameters from 9578 reflections
a = 14.0658 (4) Å	θ = 4.6–66.5°
b = 9.5990 (3) Å	µ = 6.76 mm−1
c = 11.2657 (3) Å	T = 298 K
V = 1521.07 (8) Å3	Prismatic, colourless
Z = 4	0.24 × 0.14 × 0.10 mm

Bruker APEXII CCD area-detector diffractometer	2170 independent reflections
Radiation source: fine-focus sealed tube	2153 reflections with I > 2σ(I)
graphite	Rint = 0.048
phi and ω scans	θmax = 66.5°, θmin = 4.6°
Absorption correction: multi-scan (SADABS; Bruker, 2006)	h = −16→16
Tmin = 0.370, Tmax = 0.509	k = −11→11
10215 measured reflections	l = −10→13

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)] = 0.029	H-atom parameters constrained
wR(F2) = 0.075	w = 1/[σ2(Fo2) + (0.0448P)2 + 0.2923P] where P = (Fo2 + 2Fc2)/3
S = 1.09	(Δ/σ)max = 0.001
2170 reflections	Δρmax = 0.32 e Å−3
166 parameters	Δρmin = −0.46 e Å−3
1 restraint	Absolute structure: Flack (1983), 803 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.06 (3)

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
Br1	0.76354 (2)	0.96781 (4)	0.67951 (5)	0.04630 (14)
Br2	0.94176 (3)	0.72748 (4)	0.77399 (5)	0.05922 (16)
O1	0.9457 (2)	1.4186 (4)	1.0183 (4)	0.0671 (10)
O2	0.79492 (19)	1.3427 (3)	0.9957 (3)	0.0429 (6)
O3	0.9590 (2)	0.9175 (4)	1.0552 (3)	0.0605 (8)
C1	0.9148 (3)	1.2311 (3)	0.8856 (4)	0.0368 (7)
C2	0.8510 (2)	1.1346 (3)	0.8551 (3)	0.0359 (7)
H2	0.7890	1.1450	0.8824	0.043*
C3	0.8733 (2)	1.0108 (3)	0.7796 (4)	0.0350 (7)
H3	0.9285	1.0313	0.7294	0.042*
C4	0.8964 (3)	0.8890 (4)	0.8617 (3)	0.0403 (7)
H4	0.8391	0.8632	0.9060	0.048*
C5	0.9749 (3)	0.9286 (4)	0.9494 (4)	0.0403 (8)
C6	1.0669 (3)	0.9841 (5)	0.9021 (4)	0.0481 (10)
H6B	1.0700	0.9652	0.8176	0.058*
H6A	1.1189	0.9347	0.9398	0.058*
C7	1.0806 (3)	1.1419 (5)	0.9221 (5)	0.0503 (10)
H7B	1.0685	1.1627	1.0050	0.060*
H7A	1.1463	1.1655	0.9057	0.060*
C8	1.0164 (3)	1.2335 (4)	0.8455 (4)	0.0455 (9)
H8B	1.0396	1.3286	0.8479	0.055*
H8A	1.0197	1.2018	0.7638	0.055*
C9	0.8876 (3)	1.3426 (3)	0.9735 (3)	0.0407 (8)
C10	0.7509 (3)	1.4418 (4)	1.0807 (5)	0.0488 (10)
C11	0.7934 (4)	1.4216 (6)	1.2022 (4)	0.0701 (13)
H11A	0.7917	1.3246	1.2227	0.105*
H11B	0.7576	1.4740	1.2594	0.105*
H11C	0.8581	1.4534	1.2020	0.105*
C12	0.7647 (6)	1.5884 (5)	1.0332 (7)	0.086 (2)
H12A	0.8314	1.6092	1.0295	0.130*
H12B	0.7338	1.6537	1.0849	0.130*
H12C	0.7377	1.5950	0.9552	0.130*
C13	0.6482 (4)	1.3957 (6)	1.0791 (6)	0.0723 (14)
H13A	0.6223	1.4091	1.0011	0.108*
H13B	0.6125	1.4497	1.1353	0.108*
H13C	0.6444	1.2988	1.1000	0.108*

	U11	U22	U33	U12	U13	U23
Br1	0.0408 (2)	0.0566 (2)	0.0415 (2)	−0.00053 (14)	−0.0054 (2)	−0.01174 (18)
Br2	0.0757 (3)	0.0393 (2)	0.0626 (3)	0.01023 (16)	−0.0059 (2)	−0.0133 (2)
O1	0.0599 (18)	0.0619 (19)	0.079 (3)	−0.0142 (15)	0.0064 (16)	−0.0333 (17)
O2	0.0436 (13)	0.0401 (12)	0.0451 (15)	0.0075 (11)	0.0017 (12)	−0.0121 (11)
O3	0.0719 (19)	0.0752 (19)	0.0343 (17)	−0.0037 (15)	−0.0071 (14)	0.0051 (16)
C1	0.0403 (17)	0.0328 (15)	0.0374 (19)	0.0002 (13)	0.0039 (17)	−0.0032 (14)
C2	0.0355 (16)	0.0375 (15)	0.0347 (18)	0.0076 (13)	0.0050 (14)	−0.0044 (14)
C3	0.0347 (17)	0.0374 (14)	0.0330 (17)	−0.0026 (13)	0.0021 (16)	−0.0025 (15)
C4	0.0439 (18)	0.0394 (15)	0.038 (2)	−0.0016 (14)	0.0021 (17)	−0.0007 (14)
C5	0.0402 (19)	0.0435 (16)	0.037 (2)	0.0070 (16)	−0.0026 (16)	−0.0026 (16)
C6	0.0339 (19)	0.057 (2)	0.054 (3)	0.0070 (16)	−0.0030 (17)	−0.0068 (19)
C7	0.0347 (17)	0.060 (2)	0.056 (3)	−0.0034 (17)	0.0025 (17)	−0.0164 (19)
C8	0.044 (2)	0.0453 (17)	0.047 (2)	−0.0076 (15)	0.0098 (17)	−0.0082 (15)
C9	0.050 (2)	0.0352 (15)	0.037 (2)	0.0011 (15)	0.0018 (16)	−0.0017 (14)
C10	0.066 (2)	0.0397 (17)	0.040 (2)	0.0135 (17)	0.009 (2)	−0.0088 (18)
C11	0.088 (3)	0.082 (3)	0.041 (3)	−0.001 (3)	0.006 (2)	−0.006 (2)
C12	0.138 (5)	0.038 (2)	0.083 (4)	0.026 (3)	0.038 (4)	0.002 (2)
C13	0.063 (3)	0.076 (3)	0.078 (4)	0.019 (2)	0.005 (3)	−0.023 (3)

Br1—C3	1.956 (4)	C6—H6A	0.9700
Br2—C4	1.946 (4)	C7—C8	1.528 (7)
O1—C9	1.206 (5)	C7—H7B	0.9700
O2—C9	1.328 (5)	C7—H7A	0.9700
O2—C10	1.486 (5)	C8—H8B	0.9700
O3—C5	1.217 (5)	C8—H8A	0.9700
C1—C2	1.334 (5)	C10—C11	1.507 (7)
C1—C8	1.499 (5)	C10—C13	1.511 (7)
C1—C9	1.508 (5)	C10—C12	1.518 (7)
C2—C3	1.495 (5)	C11—H11A	0.9600
C2—H2	0.9300	C11—H11B	0.9600
C3—C4	1.526 (5)	C11—H11C	0.9600
C3—H3	0.9800	C12—H12A	0.9600
C4—C5	1.529 (6)	C12—H12B	0.9600
C4—H4	0.9800	C12—H12C	0.9600
C5—C6	1.498 (6)	C13—H13A	0.9600
C6—C7	1.543 (6)	C13—H13B	0.9600
C6—H6B	0.9700	C13—H13C	0.9600
C9—O2—C10	122.1 (3)	C1—C8—C7	112.6 (4)
C2—C1—C8	125.0 (3)	C1—C8—H8B	109.1
C2—C1—C9	119.5 (3)	C7—C8—H8B	109.1
C8—C1—C9	115.4 (3)	C1—C8—H8A	109.1
C1—C2—C3	123.9 (3)	C7—C8—H8A	109.1
C1—C2—H2	118.1	H8B—C8—H8A	107.8
C3—C2—H2	118.1	O1—C9—O2	125.9 (3)
C2—C3—C4	108.0 (3)	O1—C9—C1	122.2 (3)
C2—C3—Br1	109.3 (2)	O2—C9—C1	111.9 (3)
C4—C3—Br1	110.8 (2)	O2—C10—C11	109.7 (4)
C2—C3—H3	109.6	O2—C10—C13	101.7 (4)
C4—C3—H3	109.6	C11—C10—C13	110.7 (5)
Br1—C3—H3	109.6	O2—C10—C12	108.3 (4)
C3—C4—C5	110.8 (3)	C11—C10—C12	112.9 (5)
C3—C4—Br2	111.9 (3)	C13—C10—C12	113.0 (5)
C5—C4—Br2	106.8 (2)	C10—C11—H11A	109.5
C3—C4—H4	109.1	C10—C11—H11B	109.5
C5—C4—H4	109.1	H11A—C11—H11B	109.5
Br2—C4—H4	109.1	C10—C11—H11C	109.5
O3—C5—C6	122.5 (4)	H11A—C11—H11C	109.5
O3—C5—C4	118.6 (4)	H11B—C11—H11C	109.5
C6—C5—C4	118.9 (3)	C10—C12—H12A	109.5
C5—C6—C7	113.9 (3)	C10—C12—H12B	109.5
C5—C6—H6B	108.8	H12A—C12—H12B	109.5
C7—C6—H6B	108.8	C10—C12—H12C	109.5
C5—C6—H6A	108.8	H12A—C12—H12C	109.5
C7—C6—H6A	108.8	H12B—C12—H12C	109.5
H6B—C6—H6A	107.7	C10—C13—H13A	109.5
C8—C7—C6	114.1 (4)	C10—C13—H13B	109.5
C8—C7—H7B	108.7	H13A—C13—H13B	109.5
C6—C7—H7B	108.7	C10—C13—H13C	109.5
C8—C7—H7A	108.7	H13A—C13—H13C	109.5
C6—C7—H7A	108.7	H13B—C13—H13C	109.5
H7B—C7—H7A	107.6

D—H···A	D—H	H···A	D···A	D—H···A
C3—H3···O3i	0.98	2.57	3.525 (5)	165.
C8—H8A···O3i	0.97	2.63	3.590 (6)	172.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C3—H3⋯O3i	0.98	2.57	3.525 (5)	165
C8—H8A⋯O3i	0.97	2.63	3.590 (6)	172

Symmetry code: (i) .