5-Butyl­thevinone: stereochemistry of the Diels–Alder reaction of 5-butyl­thebaine with 3-buten-2-one

Chen, W.; Metcalf, M.D.; Coop, A.; Flippen-Anderson, J.L.; Deschamps, J.R.

doi:10.1107/S1600536802023413

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5-Butylthevinone: stereochemistry of the Diels–Alder reaction of 5-butylthebaine with 3-buten-2-one

W. Chen, M. D. Metcalf, A. Coop, J. L. Flippen-Anderson and J. R. Deschamps

In this paper, we report on the X-ray analysis of 5-butylthevinone (7α-acetyl-4,5α-epoxy-3,6-dimethoxy-5β-butyl-17-methyl-6α,14α-ethenoisomorphinan), C₂₇H₃₅NO₄. This compound is the sole product of a Diels–Alder reaction of 5-butylthebaine with 3-buten-2-one, through attack of the dienophile on the β-face of the diene, even though it has been suggested that the introduction of 5β-substituents tends to hinder attack from the β-face, and leads to the production of exo-etheno adducts through attack from the α-face.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536802023413/ac6027sup1.cif Contains datablocks global, 3
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536802023413/ac60273sup2.hkl Contains datablock 3

CCDC reference: 204670

checkCIF report

Key indicators

Single-crystal X-ray study
T = 298 K
Mean (C-C) = 0.006 Å
R factor = 0.056
wR factor = 0.124
Data-to-parameter ratio = 12.8

checkCIF results

No syntax errors found

ADDSYM reports no extra symmetry

General Notes



REFLT_03
         From the CIF: _diffrn_reflns_theta_max           28.42
         From the CIF: _reflns_number_total               3701
         Count of symmetry unique reflns         3137
         Completeness (_total/calc)            117.98%
         TEST3: Check Friedels for noncentro structure
         Estimate of Friedel pairs measured       564
         Fraction of Friedel pairs measured     0.180
         Are heavy atom types Z>Si present           no
          ALERT: MoKa measured Friedel data cannot be used to
                 determine absolute structure in a light-atom
                 study EXCEPT under VERY special conditions.
                 It is preferred that Friedel data is merged in such cases.

Comment top

The orvinols are an important class of opioids which are of continued interest due to their high potency as analgesics (Casy & Parfitt, 1986; Maat et al., 1999; Coop et al., 2000; Derrick et al., 2000; Meada & Coop, 2001). The preparation of the orvinols involves a Diels–Alder addition of a dienophile to the diene system of thebaine, (1), which occurs from the least hindered β-face (endo-adducts). Several reports have shown that the introduction of small substituents into the 5-position of thebaine (Boden et al., 1982) hinders the β-face to attack, giving rise to a small quantity of the adduct arising from attack from the α-face (exo-adducts) (Woudenberg et al., 1992, 1994; Baas et al., 1997; Maat et al., 1999). In an attempt to brominate the 5-position of thebaine, we inadvertently obtained the 5β-butylated derivative, (2), and considered that this compound would possess greater steric hindrance than the small substituents already investigated. We hypothesized that a greater quantity of the exo-adduct would result.

As expected a slow reaction was observed, but unexpectedly the only product formed was the endo-adduct, (3), resulting from attack from the β-face. Thus, the introduction of a large β-butyl group does not favor attack from the α-face.

The title compound, (3), crystallized in the monoclinic space group P2₁ with one molecule in the asymmetric unit (Fig. 1). The absolute configuration could not be determined from the X-ray data and was therefore set based on heroin (Deschamps et al., 1996).

Experimental top

Synthesis of 5-butylthebaine, (2): to a stirred solution of TMEDA (0.78 ml, 5.1 mmol) in dry tetrahydrofuran (THF, 10 ml), cooled to 195 K, was added a solution of BuLi solution (12 ml of a 1.11 M solution in hexane, 13.3 mmol). The mixture was stirred for 30 min before the slow addition of a solution of thebaine, (1) (0.93 g, 3.0 mmol) in dry THF (20 ml). The solution was allowed to stir at 195 K for 1 h, followed by the addition of N-bromosuccinimide (0.60 g, 3.4 mmol) in THF (10 ml). After stirring for a further 30 min at 195 K, the solution was allowed to come to room temperature over 2 h, and stirred at room temperature overnight. After removal of the solvent, the residue was taken up in CHCl₃ (50 ml), washed with NaHCO₃ solution, water, and brine, dried (Na₂SO₄) and concentrated. The residue was purified by flash chromatography on silica gel (gradient from 2% to 10% MeOH in CH₂Cl₂) to afford (2) (0.61 g, 55%) as a colorless foam as the sole product. ¹H NMR (300 MHz, CDCl₃): δ 0.90 (t, 3H, J = 6.6 Hz, CH₃ in butyl group), 2.46 (s, NCH₃), 3.29 (d, 1H, J = 18.3 Hz), 3.56 (s, 3H, OMe), 3.65 (d, 1H, J = 6.1 Hz), 3.83 (s, 3H, OMe), 5.07 (d, 1H, J = 6.4 Hz), 5.55 (d, 1H, J = 6.4 Hz), 6.57 (d, 1H, J = 8.3 Hz), 6.63 (d, 1H, J = 8.3 Hz).

Synthesis of 5-butylthevinone, (3): a mixture of (2) (0.56 g, 1.52 mmol), 3-buten-2-one (4.8 ml, 57.7 mmol) and toluene (10 ml) was heated under reflux for 13 d. The reaction mixture was concentrated, and the residue was purified by flash chromatography on silica gel (gradient: 1% to 3% MeOH in CH₂Cl₂) to afford (3) (0.28 g, 42%) as a colorless solid as the only product. Evaporative recrystallization from MeOH provided crystals suitable for X-ray analysis; m.p. 456–457 K. ¹H NMR (300 MHz, CDCl₃): δ 0.93 (t, 3H, J = 6.6 Hz, CH₃ in butyl group), 2.14 (s, 3H, Me in acetyl), 2.34 (s, 3H, NMe), 3.11 (d, 1H, J = 6.4 Hz), 3.24 (d, 1H, J = 18.3 Hz), 3.58 (s, 3H, OMe), 3.82 (s, 3H, OMe), 5.48 (d, 1H, J = 8.8 Hz), 5.97 (d, 1H, J = 8.8 Hz), 6.47 (d, 1H, J = 8.0 Hz), 6.61 (d, 1H, J = 8.0 Hz). ¹³C NMR (75 MHz, CDCl₃): δ 210.10, 148.64, 141.65, 135.99, 129.29, 125.32, 119.14, 115.09, 100.34, 84.04, 60.88, 57.74, 54.86, 50.53, 49.69, 45.97, 44.83, 43.73, 32.25, 29.24 (2 C), 29.11, 28.92, 27.66, 24.16, 23.13, 14.49. EIMS m/z: 437 (M+, 47%), 394 (32%), 206 (100%).

Computing details top

Data collection: SMART (Bruker, 1999); cell refinement: SMART; data reduction: SAINT (Bruker, 2000) and XPREP (Bruker, 1997); program(s) used to solve structure: SHELXTL (Bruker, 2000); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top

Fig. 1. View of 5-butylthevinone, (3). Displacement ellipsoids are shown at the 20% probability level and H atoms have been omitted for clarity. The minor component of the disordered β-butyl side chain has been omitted for clarity.

(7α-acetyl-4,5α-epoxy-3,6-dimethoxy-5β-butyl-17-methyl-6α, 14α ethenoisomorphinan) top

Crystal data top

C₂₇H₃₅NO₄	F(000) = 472
M_r = 437.56	D_x = 1.251 Mg m⁻³
Monoclinic, P2₁	Mo Kα radiation, λ = 0.71073 Å
a = 9.706 (5) Å	Cell parameters from 1983 reflections
b = 7.292 (3) Å	θ = 2.5–23.7°
c = 16.958 (8) Å	µ = 0.08 mm⁻¹
β = 104.519 (6)°	T = 298 K
V = 1161.8 (9) Å³	Prism, colorless
Z = 2	0.64 × 0.18 × 0.06 mm

Data collection top

Bruker SMART 1000 CCD diffractometer	3701 independent reflections
Radiation source: sealed tube	2014 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.056
ϕ and ω scans	θ_max = 28.4°, θ_min = 2.2°
Absorption correction: multi-scan (Bruker, 2000)	h = −12→12
T_min = 0.921, T_max = 0.994	k = −3→9
5557 measured reflections	l = −20→22

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.056	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.124	H-atom parameters constrained
S = 0.97	w = 1/[σ²(F_o²) + (0.0467P)²] where P = (F_o² + 2F_c²)/3
3701 reflections	(Δ/σ)_max < 0.001
290 parameters	Δρ_max = 0.29 e Å⁻³
2 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₂₇H₃₅NO₄	V = 1161.8 (9) Å³
M_r = 437.56	Z = 2
Monoclinic, P2₁	Mo Kα radiation
a = 9.706 (5) Å	µ = 0.08 mm⁻¹
b = 7.292 (3) Å	T = 298 K
c = 16.958 (8) Å	0.64 × 0.18 × 0.06 mm
β = 104.519 (6)°

Data collection top

Bruker SMART 1000 CCD diffractometer	3701 independent reflections
Absorption correction: multi-scan (Bruker, 2000)	2014 reflections with I > 2σ(I)
T_min = 0.921, T_max = 0.994	R_int = 0.056
5557 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.056	2 restraints
wR(F²) = 0.124	H-atom parameters constrained
S = 0.97	Δρ_max = 0.29 e Å⁻³
3701 reflections	Δρ_min = −0.25 e Å⁻³
290 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	−0.1834 (4)	0.8561 (6)	0.1632 (2)	0.0501 (11)
H1A	−0.2769	0.8731	0.1662	0.060*
C2	−0.1304 (4)	0.9586 (5)	0.1077 (2)	0.0507 (12)
H2A	−0.1916	1.0360	0.0715	0.061*
C3	0.0102 (4)	0.9479 (5)	0.1053 (2)	0.0448 (10)
O3	0.0594 (3)	1.0706 (4)	0.05736 (15)	0.0603 (8)
C3A	0.1397 (4)	0.9919 (6)	0.0052 (2)	0.0650 (14)
H3AA	0.1705	1.0875	−0.0254	0.097*
H3AB	0.0811	0.9067	−0.0316	0.097*
H3AC	0.2213	0.9291	0.0377	0.097*
C4	0.0952 (4)	0.8220 (5)	0.15682 (19)	0.0389 (9)
O5	0.2407 (2)	0.8124 (3)	0.17438 (13)	0.0418 (7)
C5	0.2887 (4)	0.6691 (5)	0.2377 (2)	0.0388 (10)
C5A	0.3854 (4)	0.5432 (6)	0.20240 (19)	0.0497 (11)
H5AA	0.4803	0.5958	0.2159	0.060*
H5AB	0.3914	0.4259	0.2300	0.060*
C5B	0.3436 (5)	0.5085 (7)	0.1131 (2)	0.0768 (15)
H5BA	0.3559	0.6216	0.0856	0.092*
H5BB	0.2430	0.4788	0.0978	0.092*
C5C	0.4219 (6)	0.3599 (11)	0.0818 (3)	0.141 (3)
H5CA	0.3972	0.2433	0.1022	0.169*
H5CB	0.3889	0.3570	0.0229	0.169*
C5D	0.5773 (6)	0.3772 (14)	0.1037 (4)	0.179 (4)
H5DA	0.6186	0.2685	0.0873	0.268*
H5DB	0.6109	0.3927	0.1615	0.268*
H5DC	0.6042	0.4818	0.0765	0.268*
C6	0.3720 (4)	0.7631 (5)	0.3188 (2)	0.0381 (10)
O6	0.5064 (3)	0.8377 (4)	0.31458 (15)	0.0506 (7)
C6A	0.5060 (5)	1.0042 (7)	0.2724 (3)	0.0788 (15)
H6AA	0.6018	1.0371	0.2727	0.118*
H6AB	0.4648	1.0988	0.2986	0.118*
H6AC	0.4509	0.9901	0.2172	0.118*
C7	0.4064 (4)	0.6017 (5)	0.38347 (18)	0.0386 (10)
H7A	0.4453	0.4990	0.3586	0.046*
C7A	0.5211 (4)	0.6634 (5)	0.4592 (2)	0.0416 (10)
O7	0.4881 (3)	0.7283 (4)	0.51700 (16)	0.0590 (8)
C7B	0.6712 (4)	0.6286 (6)	0.4587 (2)	0.0549 (12)
H7BA	0.7328	0.6730	0.5084	0.082*
H7BB	0.6924	0.6909	0.4133	0.082*
H7BC	0.6856	0.4992	0.4539	0.082*
C8	0.2695 (3)	0.5362 (6)	0.4037 (2)	0.0432 (10)
H8A	0.2702	0.5710	0.4590	0.052*
H8B	0.2633	0.4036	0.3998	0.052*
C9	−0.0051 (4)	0.5484 (6)	0.3501 (2)	0.0433 (10)
H9A	−0.0133	0.5733	0.4055	0.052*
C10	−0.1331 (4)	0.6490 (5)	0.2890 (2)	0.0481 (11)
H10A	−0.2105	0.5621	0.2717	0.058*
H10B	−0.1667	0.7469	0.3181	0.058*
C11	−0.0981 (4)	0.7295 (5)	0.2140 (2)	0.0413 (10)
C12	0.0356 (4)	0.7049 (5)	0.20308 (19)	0.0371 (10)
C13	0.1514 (4)	0.5857 (5)	0.25500 (18)	0.0361 (9)
C14	0.1394 (4)	0.6238 (5)	0.34323 (19)	0.0371 (9)
C15	0.1294 (4)	0.3795 (5)	0.2355 (2)	0.0497 (11)
H15A	0.1211	0.3611	0.1779	0.060*
H15B	0.2129	0.3131	0.2653	0.060*
C16	−0.0018 (4)	0.2991 (6)	0.2569 (2)	0.0543 (12)
H16A	−0.0870	0.3446	0.2190	0.065*
H16B	−0.0007	0.1666	0.2520	0.065*
N17	−0.0050 (3)	0.3488 (5)	0.33974 (18)	0.0479 (9)
C17	−0.1207 (5)	0.2576 (6)	0.3647 (3)	0.0739 (14)
H17A	−0.1159	0.1280	0.3559	0.111*
H17B	−0.2102	0.3041	0.3332	0.111*
H17C	−0.1123	0.2807	0.4214	0.111*
C18	0.1592 (4)	0.8259 (5)	0.35837 (19)	0.0430 (10)
H18A	0.0918	0.8969	0.3748	0.052*
C19	0.2770 (4)	0.8971 (5)	0.34719 (19)	0.0385 (10)
H19A	0.2999	1.0205	0.3561	0.046*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.033 (2)	0.057 (3)	0.052 (2)	0.010 (2)	−0.0042 (19)	−0.013 (2)
C2	0.055 (3)	0.048 (3)	0.041 (2)	0.015 (2)	−0.001 (2)	−0.005 (2)
C3	0.057 (3)	0.038 (3)	0.036 (2)	0.004 (2)	0.0044 (19)	0.0036 (19)
O3	0.080 (2)	0.0472 (19)	0.0531 (16)	0.0137 (17)	0.0152 (15)	0.0109 (15)
C3A	0.084 (3)	0.061 (3)	0.050 (2)	0.003 (3)	0.018 (2)	0.009 (2)
C4	0.045 (2)	0.039 (2)	0.0292 (18)	0.006 (2)	0.0020 (16)	−0.0055 (18)
O5	0.0386 (15)	0.0469 (18)	0.0380 (13)	0.0068 (13)	0.0059 (11)	0.0080 (12)
C5	0.041 (2)	0.041 (3)	0.033 (2)	0.0052 (19)	0.0077 (17)	0.0040 (18)
C5A	0.049 (2)	0.057 (3)	0.041 (2)	0.011 (2)	0.0076 (18)	−0.001 (2)
C5B	0.099 (4)	0.079 (4)	0.056 (3)	0.017 (3)	0.026 (3)	−0.003 (3)
C5C	0.153 (6)	0.178 (7)	0.078 (4)	0.055 (6)	0.004 (4)	−0.033 (4)
C5D	0.101 (5)	0.280 (12)	0.158 (6)	0.012 (7)	0.037 (5)	−0.064 (8)
C6	0.034 (2)	0.039 (3)	0.040 (2)	0.0006 (19)	0.0060 (17)	0.0047 (18)
O6	0.0414 (15)	0.0484 (18)	0.0605 (16)	−0.0028 (14)	0.0100 (12)	0.0131 (15)
C6A	0.072 (3)	0.070 (4)	0.099 (3)	−0.012 (3)	0.030 (3)	0.031 (3)
C7	0.042 (2)	0.036 (2)	0.0330 (19)	0.0030 (19)	0.0011 (16)	−0.0001 (17)
C7A	0.045 (2)	0.036 (3)	0.039 (2)	0.0013 (19)	0.0016 (18)	0.0006 (18)
O7	0.0581 (17)	0.069 (2)	0.0460 (17)	0.0038 (17)	0.0053 (14)	−0.0138 (16)
C7B	0.041 (2)	0.073 (3)	0.048 (2)	0.008 (2)	0.0076 (18)	0.000 (2)
C8	0.046 (2)	0.044 (3)	0.036 (2)	−0.001 (2)	0.0043 (17)	0.0038 (19)
C9	0.040 (2)	0.047 (3)	0.042 (2)	0.006 (2)	0.0082 (17)	0.002 (2)
C10	0.040 (2)	0.050 (3)	0.053 (2)	0.001 (2)	0.0102 (18)	−0.007 (2)
C11	0.038 (2)	0.042 (3)	0.040 (2)	−0.001 (2)	0.0017 (18)	−0.0087 (19)
C12	0.039 (2)	0.039 (3)	0.0299 (19)	0.003 (2)	0.0021 (17)	−0.0057 (17)
C13	0.039 (2)	0.035 (2)	0.0328 (19)	0.0021 (18)	0.0059 (16)	−0.0002 (17)
C14	0.037 (2)	0.035 (3)	0.036 (2)	0.0017 (18)	0.0035 (16)	−0.0031 (17)
C15	0.053 (2)	0.047 (3)	0.046 (2)	0.008 (2)	0.008 (2)	−0.006 (2)
C16	0.054 (3)	0.038 (3)	0.067 (3)	−0.002 (2)	0.007 (2)	−0.008 (2)
N17	0.046 (2)	0.042 (2)	0.058 (2)	−0.0088 (17)	0.0164 (16)	0.0017 (17)
C17	0.071 (3)	0.051 (3)	0.102 (4)	−0.009 (3)	0.025 (3)	0.004 (3)
C18	0.053 (2)	0.041 (3)	0.0324 (19)	0.007 (2)	0.0069 (18)	−0.0019 (18)
C19	0.045 (2)	0.028 (2)	0.040 (2)	−0.004 (2)	0.0067 (18)	0.0049 (17)

Geometric parameters (Å, º) top

C1—C11	1.386 (5)	C7—C7A	1.541 (5)
C1—C2	1.397 (5)	C7—C8	1.530 (4)
C1—H1A	0.9300	C7—H7A	0.9800
C2—C3	1.378 (5)	C7A—O7	1.201 (4)
C2—H2A	0.9300	C7A—C7B	1.481 (5)
C3—O3	1.373 (4)	C7B—H7BA	0.9600
C3—C4	1.387 (5)	C7B—H7BB	0.9600
O3—C3A	1.437 (4)	C7B—H7BC	0.9600
C3A—H3AA	0.9600	C8—C14	1.551 (5)
C3A—H3AB	0.9600	C8—H8A	0.9700
C3A—H3AC	0.9600	C8—H8B	0.9700
C4—O5	1.370 (4)	C9—N17	1.466 (5)
C4—C12	1.381 (5)	C9—C14	1.537 (5)
O5—C5	1.487 (4)	C9—C10	1.584 (5)
C5—C5A	1.537 (5)	C9—H9A	0.9800
C5—C13	1.559 (5)	C10—C11	1.516 (5)
C5—C6	1.569 (5)	C10—H10A	0.9700
C5A—C5B	1.488 (5)	C10—H10B	0.9700
C5A—H5AA	0.9700	C11—C12	1.367 (5)
C5A—H5AB	0.9700	C12—C13	1.516 (5)
C5B—C5C	1.495 (7)	C13—C15	1.543 (6)
C5B—H5BA	0.9700	C13—C14	1.555 (4)
C5B—H5BB	0.9700	C14—C18	1.501 (5)
C5C—C5D	1.466 (4)	C15—C16	1.527 (5)
C5C—H5CA	0.9700	C15—H15A	0.9700
C5C—H5CB	0.9700	C15—H15B	0.9700
C5D—H5DA	0.9600	C16—N17	1.458 (5)
C5D—H5DB	0.9600	C16—H16A	0.9700
C5D—H5DC	0.9600	C16—H16B	0.9700
C6—O6	1.432 (4)	N17—C17	1.456 (5)
C6—C19	1.502 (5)	C17—H17A	0.9600
C6—C7	1.586 (5)	C17—H17B	0.9600
O6—C6A	1.408 (5)	C17—H17C	0.9600
C6A—H6AA	0.9600	C18—C19	1.312 (5)
C6A—H6AB	0.9600	C18—H18A	0.9300
C6A—H6AC	0.9600	C19—H19A	0.9300

C11—C1—C2	120.8 (3)	C7B—C7A—C7	116.7 (3)
C11—C1—H1A	119.6	C7A—C7B—H7BA	109.5
C2—C1—H1A	119.6	C7A—C7B—H7BB	109.5
C3—C2—C1	121.6 (4)	H7BA—C7B—H7BB	109.5
C3—C2—H2A	119.2	C7A—C7B—H7BC	109.5
C1—C2—H2A	119.2	H7BA—C7B—H7BC	109.5
O3—C3—C2	118.3 (3)	H7BB—C7B—H7BC	109.5
O3—C3—C4	124.4 (4)	C7—C8—C14	109.4 (3)
C2—C3—C4	117.1 (4)	C7—C8—H8A	109.8
C3—O3—C3A	115.3 (3)	C14—C8—H8A	109.8
O3—C3A—H3AA	109.5	C7—C8—H8B	109.8
O3—C3A—H3AB	109.5	C14—C8—H8B	109.8
H3AA—C3A—H3AB	109.5	H8A—C8—H8B	108.2
O3—C3A—H3AC	109.5	N17—C9—C14	108.5 (3)
H3AA—C3A—H3AC	109.5	N17—C9—C10	113.9 (3)
H3AB—C3A—H3AC	109.5	C14—C9—C10	111.4 (3)
O5—C4—C12	113.6 (3)	N17—C9—H9A	107.6
O5—C4—C3	126.0 (4)	C14—C9—H9A	107.6
C12—C4—C3	120.0 (3)	C10—C9—H9A	107.6
C4—O5—C5	108.2 (3)	C11—C10—C9	115.1 (3)
O5—C5—C5A	104.5 (3)	C11—C10—H10A	108.5
O5—C5—C13	106.4 (3)	C9—C10—H10A	108.5
C5A—C5—C13	118.4 (3)	C11—C10—H10B	108.5
O5—C5—C6	109.0 (3)	C9—C10—H10B	108.5
C5A—C5—C6	111.8 (3)	H10A—C10—H10B	107.5
C13—C5—C6	106.4 (3)	C12—C11—C1	116.3 (4)
C5B—C5A—C5	117.4 (3)	C12—C11—C10	118.8 (3)
C5B—C5A—H5AA	107.9	C1—C11—C10	123.7 (3)
C5—C5A—H5AA	107.9	C11—C12—C4	122.8 (4)
C5B—C5A—H5AB	107.9	C11—C12—C13	126.0 (3)
C5—C5A—H5AB	107.9	C4—C12—C13	109.2 (3)
H5AA—C5A—H5AB	107.2	C12—C13—C15	113.1 (3)
C5A—C5B—C5C	116.9 (4)	C12—C13—C14	103.5 (3)
C5A—C5B—H5BA	108.1	C15—C13—C14	109.9 (3)
C5C—C5B—H5BA	108.1	C12—C13—C5	102.2 (3)
C5A—C5B—H5BB	108.1	C15—C13—C5	114.7 (3)
C5C—C5B—H5BB	108.1	C14—C13—C5	112.7 (3)
H5BA—C5B—H5BB	107.3	C18—C14—C9	114.8 (3)
C5D—C5C—C5B	115.5 (6)	C18—C14—C8	104.1 (3)
C5D—C5C—H5CA	108.4	C9—C14—C8	114.2 (3)
C5B—C5C—H5CA	108.4	C18—C14—C13	107.6 (3)
C5D—C5C—H5CB	108.4	C9—C14—C13	107.4 (3)
C5B—C5C—H5CB	108.4	C8—C14—C13	108.5 (3)
H5CA—C5C—H5CB	107.5	C16—C15—C13	113.7 (3)
C5C—C5D—H5DA	109.5	C16—C15—H15A	108.8
C5C—C5D—H5DB	109.5	C13—C15—H15A	108.8
H5DA—C5D—H5DB	109.5	C16—C15—H15B	108.8
C5C—C5D—H5DC	109.5	C13—C15—H15B	108.8
H5DA—C5D—H5DC	109.5	H15A—C15—H15B	107.7
H5DB—C5D—H5DC	109.5	N17—C16—C15	110.7 (3)
O6—C6—C19	114.1 (3)	N17—C16—H16A	109.5
O6—C6—C5	113.4 (3)	C15—C16—H16A	109.5
C19—C6—C5	110.0 (3)	N17—C16—H16B	109.5
O6—C6—C7	106.3 (3)	C15—C16—H16B	109.5
C19—C6—C7	107.5 (3)	H16A—C16—H16B	108.1
C5—C6—C7	104.8 (3)	C17—N17—C16	111.7 (3)
C6A—O6—C6	117.8 (3)	C17—N17—C9	113.2 (3)
O6—C6A—H6AA	109.5	C16—N17—C9	111.3 (3)
O6—C6A—H6AB	109.5	N17—C17—H17A	109.5
H6AA—C6A—H6AB	109.5	N17—C17—H17B	109.5
O6—C6A—H6AC	109.5	H17A—C17—H17B	109.5
H6AA—C6A—H6AC	109.5	N17—C17—H17C	109.5
H6AB—C6A—H6AC	109.5	H17A—C17—H17C	109.5
C7A—C7—C8	113.0 (3)	H17B—C17—H17C	109.5
C7A—C7—C6	110.0 (3)	C19—C18—C14	116.3 (4)
C8—C7—C6	110.0 (3)	C19—C18—H18A	121.9
C7A—C7—H7A	107.9	C14—C18—H18A	121.9
C8—C7—H7A	107.9	C18—C19—C6	114.6 (3)
C6—C7—H7A	107.9	C18—C19—H19A	122.7
O7—C7A—C7B	122.4 (3)	C6—C19—H19A	122.7
O7—C7A—C7	120.7 (3)

Experimental details

Crystal data
Chemical formula	C₂₇H₃₅NO₄
M_r	437.56
Crystal system, space group	Monoclinic, P2₁
Temperature (K)	298
a, b, c (Å)	9.706 (5), 7.292 (3), 16.958 (8)
β (°)	104.519 (6)
V (Å³)	1161.8 (9)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.64 × 0.18 × 0.06

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (Bruker, 2000)
T_min, T_max	0.921, 0.994
No. of measured, independent and observed [I > 2σ(I)] reflections	5557, 3701, 2014
R_int	0.056
(sin θ/λ)_max (Å⁻¹)	0.670

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.056, 0.124, 0.97
No. of reflections	3701
No. of parameters	290
No. of restraints	2
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.29, −0.25

Computer programs: SMART (Bruker, 1999), SMART, SAINT (Bruker, 2000) and XPREP (Bruker, 1997), SHELXTL (Bruker, 2000), SHELXTL.

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