(1R,1′R,3S,3′S)-5,5′,10,10′-Tetra­meth­oxy-1,1′,3,3′-tetra­methyl-3,3′,4,4′-tetra­hydro-1H,1′H-8,8′-bi[benzo[g]isochromene]

Sejberg, J.J.P.; Sperry, J.; Choi, K.W.; Boyd, P.D.W.; Brimble, M.A.

doi:10.1107/S1600536808007599

organic compounds

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ISSN: 2056-9890

Volume 64| Part 4| April 2008| Page o758

doi:10.1107/S1600536808007599

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(1R,1′R,3S,3′S)-5,5′,10,10′-Tetramethoxy-1,1′,3,3′-tetramethyl-3,3′,4,4′-tetrahydro-1H,1′H-8,8′-bi[benzo[g]isochromene]

Jimmy J. P. Sejberg,^a Jonathan Sperry,^a Ka Wai Choi,^a Peter D. W. Boyd ^a and Margaret A. Brimble ^a ^*

^aDepartment of Chemistry, University of Auckland, Private Bag 92019, Auckland, New Zealand
^*Correspondence e-mail: m.brimble@auckland.ac.nz

(Received 22 February 2008; accepted 19 March 2008; online 29 March 2008)

In the title compound, C₃₄H₃₈O₆, the methyl groups on each pyran ring exhibit 1,3-cis stereochemistry, established during synthesis by pseudo-axial delivery of hydride during a lactol reduction step. In the crystal structure, the molecule lies on a twofold rotation axis and the torsion angle about the central diaryl bond is 41.3 (1)°. The molecules pack in a herringbone arrangement.

Related literature

For details of the synthesis, see: Brimble et al. (2008 ). For related literature, see: Brenstrum et al. (2001 ); Gibson et al. (2007 ); Gill et al. (1997a ,b ).

Experimental

Crystal data

C₃₄H₃₈O₆
M_r = 542.64
Orthorhombic, C 222₁
a = 8.8773 (2) Å
b = 13.9298 (2) Å
c = 23.1234 (4) Å
V = 2859.42 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 89 (2) K
0.36 × 0.28 × 0.22 mm

Data collection

Siemens SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.889, T_max = 0.981
22789 measured reflections
2035 independent reflections
1542 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.095
S = 1.13
2035 reflections
185 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: SMART (Siemens, 1995 ); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ) and Mercury (Macrae et al., 2006 ); software used to prepare material for publication: publCIF (Westrip, 2008 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808007599/bi2283sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808007599/bi2283Isup2.hkl

checkCIF report

Comment top

Recent synthetic effort has been directed towards enantioselective synthesis of the dimeric pyranonaphthoquinone core of the cardinalins which were isolated from the New Zealand toadstool Dermocybe cardinalis (Gill et al., 1997a, 1997b). We now report the crystal structure of the title compound (Fig. 1). The assignment of absolute stereochemistry is based on the initial use of a chiral pool reagent in the synthetic sequence. Since the stereochemistry at C3 in the pyran rings (C12 in the crystallographic numbering scheme; Fig. 2) is known to be S, the absolute configuration at C1 (C13 in the crystallographic numbering scheme) has therefore been assigned as R. The torsion angle about the diaryl bond is 41.3 (1)°. The molecules pack in a herringbone arrangement (Fig. 3).

Related literature top

For synthesis details, see: Brimble et al. (2008). For related literature, see: Brenstrum et al. (2001); Gibson et al. (2007); Gill et al. (1997a,b).

Experimental top

To a solution of 1,1'-(6,6'-bis((S)-2-(tert-butyldiphenylsilyloxy)propyl)-5,5',8,8'-tetramethoxy-2,2'-binaphthyl-7,7'-diyl)diethanone (144 mg, 0.14 mmol) in THF (5 ml) was added a 1 M solution of tetra-n-butylammonium fluoride (3.0 ml, 3.0 mmol). The reaction mixture was stirred under nitrogen at room temperature for 3 d then concentrated in vacuo. The resulting residue was flushed through a pad of silica (hexanes-ethyl acetate 1:1–1:3). The filtrate was concentrated in vacuo and the resulting oil was dissolved in distilled dichloromethane (5 ml) and cooled to 195.15 K. Trifluoroacetic acid (0.065 ml, 0.86 mmol) was added and the reaction mixture was stirred for 15 min before addition of triethylsilane (0.13 ml, 0.80 mmol). The reaction mixture was then allowed to reach room temperature over 16 h. Water (20 ml) was added and the mixture extracted with ethyl acetate (20 ml × 3). The combined organic extracts were dried over anhydrous magnesium sulfate, filtered, concentrated in vacuo and the resulting residue was purified by flash chromatography eluting with hexanes-ethyl acetate (7:3) to give the title compound (52 mg, 0.096 mmol, 70%) as a pale yellow solid which was recrystallized from diethyl ether-dichloromethane; m.p. 541.15–542.15 K

Computing details top

Data collection: SMART (Siemens, 1995); cell refinement: SAINT (Siemens, 1995); data reduction: SAINT (Siemens, 1995); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006); software used to prepare material for publication: publCIF (Westrip, 2008).

Figures top

	Fig. 1. Scheme showing the standard chemical numbering scheme.
	Fig. 2. The molecular structure with displacement ellipsoids drawn at the 50% probability level for non-H atoms, showing the crystallographic numbering scheme. Symmetry code: (i) x, -y, 1 - z.
	Fig. 3. Molecular packing viewed down the a-axis, with H atoms omitted.

(1R,1'R,3S,3'S)-5,5',10,10'-Tetramethoxy-1,1',3,3'- tetramethyl- 3,3',4,4'-tetrahydro-1H,1'H-8,8'-bi[benzo[g]isochromene] top

Crystal data top

C₃₄H₃₈O₆	D_x = 1.261 Mg m⁻³
M_r = 542.64	Melting point: 541.15 K
Orthorhombic, C222₁	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C 2c 2	Cell parameters from 4238 reflections
a = 8.8773 (2) Å	θ = 1.8–28.6°
b = 13.9298 (2) Å	µ = 0.09 mm⁻¹
c = 23.1234 (4) Å	T = 89 K
V = 2859.42 (9) Å³	Needle, pale yellow
Z = 4	0.36 × 0.28 × 0.22 mm
F(000) = 1160

Data collection top

Siemens SMART CCD diffractometer	2035 independent reflections
Radiation source: fine-focus sealed tube	1542 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
ω scans	θ_max = 28.6°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −11→11
T_min = 0.889, T_max = 0.981	k = −18→18
22789 measured reflections	l = −27→30

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.095	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.0484P)² + 0.1354P] where P = (F_o² + 2F_c²)/3
2035 reflections	(Δ/σ)_max < 0.001
185 parameters	Δρ_max = 0.21 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₃₄H₃₈O₆	V = 2859.42 (9) Å³
M_r = 542.64	Z = 4
Orthorhombic, C222₁	Mo Kα radiation
a = 8.8773 (2) Å	µ = 0.09 mm⁻¹
b = 13.9298 (2) Å	T = 89 K
c = 23.1234 (4) Å	0.36 × 0.28 × 0.22 mm

Data collection top

Siemens SMART CCD diffractometer	2035 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1542 reflections with I > 2σ(I)
T_min = 0.889, T_max = 0.981	R_int = 0.052
22789 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.095	H-atom parameters constrained
S = 1.13	Δρ_max = 0.21 e Å⁻³
2035 reflections	Δρ_min = −0.19 e Å⁻³
185 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
O2	0.81372 (17)	0.37827 (10)	0.59844 (6)	0.0305 (4)
O1	0.33079 (16)	0.12481 (10)	0.60649 (6)	0.0293 (4)
O3	0.29982 (17)	0.39411 (11)	0.69152 (7)	0.0340 (4)
C4	0.7076 (2)	0.22511 (15)	0.57426 (9)	0.0249 (5)
C2	0.8442 (2)	0.11042 (16)	0.51523 (9)	0.0264 (5)
H2	0.9313	0.0936	0.4953	0.032*
C1	0.7206 (2)	0.04620 (15)	0.51579 (8)	0.0240 (5)
C9	0.4425 (2)	0.27435 (16)	0.63512 (9)	0.0259 (5)
C5	0.5831 (2)	0.16126 (15)	0.57533 (9)	0.0235 (4)
C7	0.6948 (2)	0.31407 (15)	0.60336 (9)	0.0260 (5)
C3	0.8384 (2)	0.19642 (15)	0.54331 (9)	0.0257 (5)
H3	0.9215	0.2370	0.5422	0.031*
C10	0.4513 (2)	0.18827 (15)	0.60595 (9)	0.0254 (5)
C6	0.5934 (2)	0.07262 (14)	0.54638 (9)	0.0243 (5)
H6	0.5122	0.0305	0.5479	0.029*
C11	0.5454 (3)	0.43732 (15)	0.65890 (10)	0.0312 (5)
H11A	0.6029	0.4843	0.6372	0.037*
H11B	0.5819	0.4371	0.6984	0.037*
C8	0.5659 (2)	0.33918 (16)	0.63246 (9)	0.0267 (5)
C13	0.2982 (3)	0.29950 (16)	0.66695 (9)	0.0314 (5)
H13	0.2144	0.2957	0.6395	0.038*
C12	0.3790 (3)	0.46387 (17)	0.65792 (10)	0.0354 (6)
H12	0.3422	0.4622	0.6180	0.043*
C17	0.3459 (3)	0.56069 (17)	0.68390 (11)	0.0430 (7)
H17A	0.2397	0.5733	0.6816	0.065*
H17B	0.3999	0.6093	0.6630	0.065*
H17C	0.3768	0.5612	0.7237	0.065*
C15	0.9036 (3)	0.3855 (2)	0.64991 (10)	0.0382 (6)
H15A	0.8431	0.4102	0.6809	0.057*
H15B	0.9868	0.4281	0.6430	0.057*
H15C	0.9411	0.3232	0.6601	0.057*
C14	0.2395 (3)	0.12913 (18)	0.55544 (10)	0.0382 (6)
H14A	0.1977	0.1924	0.5516	0.057*
H14B	0.1594	0.0831	0.5583	0.057*
H14C	0.3003	0.1148	0.5222	0.057*
C16	0.2646 (3)	0.23321 (17)	0.71690 (10)	0.0427 (6)
H16A	0.3452	0.2365	0.7445	0.064*
H16B	0.2552	0.1686	0.7029	0.064*
H16C	0.1721	0.2524	0.7350	0.064*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O2	0.0365 (9)	0.0286 (8)	0.0265 (8)	−0.0083 (7)	−0.0003 (7)	0.0009 (7)
O1	0.0278 (8)	0.0357 (8)	0.0244 (8)	−0.0046 (7)	0.0007 (6)	0.0002 (7)
O3	0.0385 (9)	0.0344 (9)	0.0292 (9)	0.0067 (8)	0.0023 (7)	−0.0034 (7)
C4	0.0283 (11)	0.0256 (11)	0.0208 (11)	0.0011 (9)	−0.0019 (8)	0.0030 (9)
C2	0.0239 (10)	0.0329 (12)	0.0224 (12)	−0.0005 (9)	0.0010 (8)	0.0024 (10)
C1	0.0284 (10)	0.0243 (11)	0.0194 (11)	0.0012 (9)	−0.0028 (8)	0.0035 (9)
C9	0.0309 (11)	0.0291 (12)	0.0178 (10)	0.0024 (9)	0.0001 (8)	0.0027 (9)
C5	0.0266 (10)	0.0245 (11)	0.0194 (11)	0.0015 (9)	−0.0014 (8)	0.0034 (9)
C7	0.0318 (11)	0.0236 (11)	0.0226 (11)	−0.0019 (9)	−0.0018 (9)	0.0035 (9)
C3	0.0249 (10)	0.0276 (12)	0.0247 (11)	−0.0038 (9)	−0.0004 (9)	0.0030 (9)
C10	0.0255 (11)	0.0286 (11)	0.0221 (10)	−0.0008 (9)	−0.0006 (8)	0.0050 (10)
C6	0.0255 (10)	0.0256 (11)	0.0218 (11)	−0.0024 (9)	−0.0023 (9)	0.0020 (9)
C11	0.0412 (13)	0.0235 (11)	0.0288 (12)	0.0012 (10)	0.0022 (10)	0.0005 (10)
C8	0.0346 (11)	0.0261 (11)	0.0193 (11)	0.0031 (9)	−0.0015 (9)	0.0048 (9)
C13	0.0316 (12)	0.0336 (13)	0.0289 (12)	0.0051 (10)	0.0021 (9)	−0.0043 (10)
C12	0.0504 (14)	0.0315 (13)	0.0243 (12)	0.0103 (11)	−0.0012 (10)	0.0012 (11)
C17	0.0602 (16)	0.0371 (14)	0.0318 (14)	0.0160 (12)	−0.0048 (12)	−0.0012 (12)
C15	0.0364 (13)	0.0429 (14)	0.0354 (14)	−0.0068 (11)	−0.0038 (11)	−0.0004 (12)
C14	0.0303 (12)	0.0498 (16)	0.0346 (14)	−0.0090 (11)	−0.0032 (10)	0.0045 (12)
C16	0.0480 (14)	0.0448 (15)	0.0354 (13)	−0.0002 (12)	0.0158 (12)	−0.0041 (12)

Geometric parameters (Å, º) top

O2—C7	1.388 (2)	C6—H6	0.9300
O2—C15	1.436 (3)	C11—C8	1.509 (3)
O1—C10	1.388 (2)	C11—C12	1.523 (3)
O1—C14	1.433 (3)	C11—H11A	0.9700
O3—C12	1.429 (3)	C11—H11B	0.9700
O3—C13	1.435 (3)	C13—C16	1.508 (3)
C4—C7	1.415 (3)	C13—H13	0.9800
C4—C3	1.421 (3)	C12—C17	1.505 (3)
C4—C5	1.419 (3)	C12—H12	0.9800
C2—C3	1.364 (3)	C17—H17A	0.9600
C2—C1	1.416 (3)	C17—H17B	0.9600
C2—H2	0.9300	C17—H17C	0.9600
C1—C6	1.382 (3)	C15—H15A	0.9600
C1—C1ⁱ	1.480 (4)	C15—H15B	0.9600
C9—C10	1.378 (3)	C15—H15C	0.9600
C9—C8	1.421 (3)	C14—H14A	0.9600
C9—C13	1.518 (3)	C14—H14B	0.9600
C5—C6	1.408 (3)	C14—H14C	0.9600
C5—C10	1.418 (3)	C16—H16A	0.9600
C7—C8	1.373 (3)	C16—H16B	0.9600
C3—H3	0.9300	C16—H16C	0.9600

C7—O2—C15	113.58 (16)	C9—C8—C11	117.76 (19)
C10—O1—C14	113.67 (15)	O3—C13—C16	105.14 (17)
C12—O3—C13	114.47 (16)	O3—C13—C9	113.29 (18)
C7—C4—C3	123.47 (19)	C16—C13—C9	113.37 (19)
C7—C4—C5	118.55 (18)	O3—C13—H13	108.3
C3—C4—C5	117.97 (18)	C16—C13—H13	108.3
C3—C2—C1	121.43 (18)	C9—C13—H13	108.3
C3—C2—H2	119.3	O3—C12—C17	107.21 (19)
C1—C2—H2	119.3	O3—C12—C11	107.70 (18)
C6—C1—C2	118.01 (18)	C17—C12—C11	113.7 (2)
C6—C1—C1ⁱ	118.94 (14)	O3—C12—H12	109.4
C2—C1—C1ⁱ	123.03 (14)	C17—C12—H12	109.4
C10—C9—C8	119.23 (18)	C11—C12—H12	109.4
C10—C9—C13	119.07 (19)	C12—C17—H17A	109.5
C8—C9—C13	121.64 (19)	C12—C17—H17B	109.5
C6—C5—C10	121.61 (19)	H17A—C17—H17B	109.5
C6—C5—C4	119.37 (18)	C12—C17—H17C	109.5
C10—C5—C4	119.02 (18)	H17A—C17—H17C	109.5
C8—C7—O2	120.66 (18)	H17B—C17—H17C	109.5
C8—C7—C4	121.54 (19)	O2—C15—H15A	109.5
O2—C7—C4	117.67 (18)	O2—C15—H15B	109.5
C2—C3—C4	121.19 (19)	H15A—C15—H15B	109.5
C2—C3—H3	119.4	O2—C15—H15C	109.5
C4—C3—H3	119.4	H15A—C15—H15C	109.5
C9—C10—O1	120.42 (18)	H15B—C15—H15C	109.5
C9—C10—C5	121.46 (19)	O1—C14—H14A	109.5
O1—C10—C5	118.11 (18)	O1—C14—H14B	109.5
C1—C6—C5	122.02 (19)	H14A—C14—H14B	109.5
C1—C6—H6	119.0	O1—C14—H14C	109.5
C5—C6—H6	119.0	H14A—C14—H14C	109.5
C8—C11—C12	109.3 (2)	H14B—C14—H14C	109.5
C8—C11—H11A	109.8	C13—C16—H16A	109.5
C12—C11—H11A	109.8	C13—C16—H16B	109.5
C8—C11—H11B	109.8	H16A—C16—H16B	109.5
C12—C11—H11B	109.8	C13—C16—H16C	109.5
H11A—C11—H11B	108.3	H16A—C16—H16C	109.5
C7—C8—C9	120.13 (19)	H16B—C16—H16C	109.5
C7—C8—C11	121.99 (19)

Symmetry code: (i) x, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₃₄H₃₈O₆
M_r	542.64
Crystal system, space group	Orthorhombic, C222₁
Temperature (K)	89
a, b, c (Å)	8.8773 (2), 13.9298 (2), 23.1234 (4)
V (Å³)	2859.42 (9)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.36 × 0.28 × 0.22

Data collection
Diffractometer	Siemens SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.889, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	22789, 2035, 1542
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.673

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.095, 1.13
No. of reflections	2035
No. of parameters	185
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.21, −0.19

Computer programs: SMART (Siemens, 1995), SAINT (Siemens, 1995), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996) and Mercury (Macrae et al., 2006), publCIF (Westrip, 2008).

Acknowledgements

Tania Groutso is gratefully acknowledged for assistance with the data collection.

References

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