(+)-3-{(4S,5S)-5-[1,1-Di­methyl-2-(phenyl­thio)­ethyl]-2,2-di­methyl-1,3-dioxolan-4-yl}prop-2-yn-1-ol

The absolute configuration was determined for the title compound, (+)-C₁₈H₂₄O₃S, (I), which was prepared in a synthetic study on the natural products, bryostatins.

S1. Comment

A synthetic study on bryostatin 3 has been reported (Obitsu et al., 1998).

S2. Experimental

The title optically active compound was prepared by the authors in a synthetic study on bryostatins (Ohmori et al., 2000). The angle of rotation [α]_D²¹ is +20.9 ° (c 1.0, CHCl₃). Crystals were grown from a hexane/ethyl acetate solution.

S3. Refinement

X-ray intensities were measured for -h+k+l (θ < 75°), +h+k-l (θ < 30°) and +h-k-l (θ < 30°). There were 163 Friedel pairs, which were not averaged. The completeness of symmetry unique reflections (θ < 75°) was 93.3%, which was due to the blind region of the low-temperature apparatus. The hydroxyl H atom was located from a difference synthesis. Their positional parameters were refined with restraint of O—H = 0.98 Å (s.u. 0.01 Å) with U_iso(H) = 1.2U_eq(parent atom). The other H-atom positional parameters were calculated geometrically and fixed with U_iso(H) = 1.2U_eq(parent atom). The absolute structure was determined based on a Flack parameter value of 0.03 (3).

Computing details

Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation, 1993); cell refinement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation, 1999); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: TEXSAN.

(I)

Crystal data

C18H24O3S	Dx = 1.208 Mg m^−3
Mr = 320.45	Cu Kα radiation, λ = 1.54184 Å
Orthorhombic, P212121	Cell parameters from 25 reflections
a = 8.760 (2) Å	θ = 29.1–30.0°
b = 32.090 (2) Å	µ = 1.71 mm^−1
c = 6.269 (2) Å	T = 248 K
V = 1762.3 (6) Å^3	Prism, colourless
Z = 4	0.5 × 0.5 × 0.3 mm

Data collection

Rigaku AFC-7R diffractometer	Rint = 0.036
θ–2θ scans	θmax = 75°, θmin = 2.5°
Absorption correction: integration (Coppens et al., 1965)	h = −11→5
Tmin = 0.476, Tmax = 0.636	k = −20→40
2633 measured reflections	l = −4→8
2147 independent reflections	3 standard reflections every 150 reflections
2055 reflections with I > 2σ(I)	intensity decay: none

Refinement

Refinement on F^2	(Δ/σ)max = 0.001
R[F^2 > 2σ(F^2)] = 0.040	Δρmax = 0.43 e Å^−3
wR(F^2) = 0.108	Δρmin = −0.41 e Å^−3
S = 1.08	Extinction correction: SHELXL97 (Sheldrick, 1997), Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
2147 reflections	Extinction coefficient: 0.0101 (6)
203 parameters	Absolute structure: Flack (1983), 163 Friedel pairs
H atoms treated by a mixture of independent and constrained refinement	Absolute structure parameter: 0.03 (3)
w = 1/[σ^2(Fo^2) + (0.0524P)^2 + 0.8338P] where P = (Fo^2 + 2Fc^2)/3

Special details

Refinement. Refinement was based on F² against all reflections. The weighted R-factor (wR) and goodness of fit (S) were based on F², and conventional R-factor (R) was calculated on F, with F set to zero for negative F². The threshold expression of I > 2σ(I) was used only for calculating R-factor(gt).

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
S1	0.8731 (1)	0.04241 (2)	0.2786 (2)	0.0772 (4)
O2	1.0693 (2)	0.13357 (5)	0.5234 (3)	0.0405 (5)
O3	1.0371 (2)	0.20060 (6)	0.4179 (4)	0.0551 (6)
O4	0.6503 (3)	0.22811 (8)	−0.2094 (4)	0.0821 (9)
C5	0.9962 (3)	−0.00085 (8)	0.2971 (5)	0.0459 (7)
C6	1.0057 (4)	−0.02559 (8)	0.4764 (5)	0.0478 (7)
C7	1.1053 (4)	−0.05906 (9)	0.4797 (6)	0.0590 (8)
C8	1.1930 (4)	−0.0689 (1)	0.3089 (8)	0.068 (1)
C9	1.1843 (4)	−0.0458 (1)	0.1305 (7)	0.070 (1)
C10	1.0870 (4)	−0.0110 (1)	0.1197 (5)	0.0644 (10)
C11	0.8674 (3)	0.06189 (8)	0.5500 (5)	0.0457 (7)
C12	0.8121 (3)	0.10762 (8)	0.5656 (5)	0.0435 (7)
C13	0.8125 (5)	0.1189 (1)	0.8022 (6)	0.066 (1)
C14	0.6509 (3)	0.1115 (1)	0.4714 (8)	0.071 (1)
C15	0.9186 (3)	0.13582 (7)	0.4367 (4)	0.0341 (6)
C16	0.8875 (3)	0.18303 (7)	0.4454 (4)	0.0363 (6)
C17	0.7843 (3)	0.19858 (7)	0.2797 (5)	0.0403 (6)
C18	0.6966 (3)	0.21124 (8)	0.1505 (5)	0.0466 (7)
C19	0.5863 (4)	0.2263 (1)	−0.0074 (6)	0.0649 (10)
C20	1.1503 (3)	0.16902 (8)	0.4481 (5)	0.0421 (6)
C21	1.2616 (4)	0.1831 (1)	0.6144 (7)	0.075 (1)
C22	1.2271 (5)	0.1602 (1)	0.2395 (8)	0.090 (1)
H4	0.596 (4)	0.2495 (10)	−0.290 (6)	0.0984*
H6	0.9414	−0.0193	0.6003	0.0519*
H7	1.1147	−0.0762	0.6067	0.0721*
H8	1.2589	−0.0929	0.3196	0.0824*
H9	1.2479	−0.0526	0.0061	0.0800*
H10	1.0848	0.0060	−0.0054	0.0766*
H11A	0.7982	0.0451	0.6332	0.0492*
H11B	0.9677	0.0602	0.6125	0.0492*
H13A	0.7494	0.1008	0.8826	0.0780*
H13B	0.9187	0.1159	0.8596	0.0780*
H13C	0.7841	0.1474	0.8240	0.0780*
H14A	0.5807	0.0938	0.5390	0.0793*
H14B	0.6544	0.1023	0.3154	0.0793*
H14C	0.6170	0.1396	0.4684	0.0793*
H15	0.9192	0.1267	0.2900	0.0398*
H16	0.8450	0.1905	0.5846	0.0407*
H19A	0.4973	0.2096	0.0001	0.0819*
H19B	0.5577	0.2549	0.0391	0.0819*
H21A	1.2119	0.1897	0.7458	0.0775*
H21B	1.3407	0.1635	0.6354	0.0775*
H21C	1.3105	0.2096	0.5637	0.0775*
H22A	1.1577	0.1513	0.1331	0.1127*
H22B	1.3042	0.1383	0.2604	0.1127*
H22C	1.2812	0.1848	0.1910	0.1127*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.1237 (9)	0.0398 (4)	0.0681 (6)	0.0140 (5)	−0.0458 (6)	−0.0045 (4)
O2	0.0351 (9)	0.0347 (8)	0.052 (1)	0.0014 (7)	−0.0054 (10)	0.0086 (8)
O3	0.043 (1)	0.0367 (9)	0.086 (2)	−0.0053 (8)	−0.006 (1)	0.021 (1)
O4	0.100 (2)	0.085 (2)	0.061 (1)	0.048 (2)	0.008 (2)	0.032 (1)
C5	0.051 (2)	0.038 (1)	0.049 (2)	−0.014 (1)	−0.003 (2)	−0.003 (1)
C6	0.054 (2)	0.037 (1)	0.053 (2)	0.002 (1)	0.008 (2)	0.002 (1)
C7	0.058 (2)	0.044 (1)	0.075 (2)	0.008 (1)	0.002 (2)	−0.002 (2)
C8	0.050 (2)	0.067 (2)	0.088 (3)	0.001 (2)	0.000 (2)	−0.025 (2)
C9	0.044 (2)	0.086 (2)	0.080 (3)	−0.015 (2)	0.019 (2)	−0.038 (2)
C10	0.075 (2)	0.071 (2)	0.047 (2)	−0.040 (2)	−0.002 (2)	0.000 (2)
C11	0.049 (2)	0.031 (1)	0.056 (2)	−0.002 (1)	−0.004 (2)	0.010 (1)
C12	0.039 (1)	0.032 (1)	0.059 (2)	0.001 (1)	0.005 (1)	0.012 (1)
C13	0.090 (3)	0.047 (2)	0.060 (2)	0.009 (2)	0.036 (2)	0.013 (2)
C14	0.035 (1)	0.053 (2)	0.126 (4)	−0.003 (1)	0.001 (2)	0.029 (2)
C15	0.033 (1)	0.030 (1)	0.039 (1)	0.0024 (10)	−0.003 (1)	0.004 (1)
C16	0.037 (1)	0.031 (1)	0.041 (1)	0.001 (1)	0.001 (1)	0.005 (1)
C17	0.042 (1)	0.033 (1)	0.046 (1)	0.004 (1)	0.001 (1)	0.007 (1)
C18	0.044 (1)	0.043 (1)	0.053 (2)	0.005 (1)	0.001 (2)	0.010 (1)
C19	0.050 (2)	0.086 (2)	0.059 (2)	0.012 (2)	−0.001 (2)	0.024 (2)
C20	0.036 (1)	0.037 (1)	0.053 (2)	−0.003 (1)	0.001 (1)	0.002 (1)
C21	0.070 (2)	0.055 (2)	0.100 (3)	−0.009 (2)	−0.035 (2)	0.003 (2)
C22	0.093 (3)	0.075 (2)	0.101 (3)	−0.021 (2)	0.051 (3)	−0.012 (2)

Geometric parameters (Å, º)

S1—C5	1.762 (3)	C12—C15	1.531 (4)
S1—C11	1.813 (3)	C13—H13A	0.95
O2—C15	1.429 (3)	C13—H13B	1.00
O2—C20	1.422 (3)	C13—H13C	0.96
O3—C16	1.437 (3)	C14—H14A	0.94
O3—C20	1.431 (3)	C14—H14B	1.02
O4—C19	1.386 (4)	C14—H14C	0.95
O4—H4	0.98 (3)	C15—C16	1.540 (3)
C5—C6	1.378 (4)	C15—H15	0.97
C5—C10	1.405 (5)	C16—C17	1.465 (4)
C6—C7	1.384 (4)	C16—H16	0.98
C6—H6	0.98	C17—C18	1.188 (4)
C7—C8	1.355 (6)	C18—C19	1.465 (5)
C7—H7	0.97	C19—H19A	0.95
C8—C9	1.344 (6)	C19—H19B	1.00
C8—H8	0.97	C20—C21	1.497 (5)
C9—C10	1.406 (5)	C20—C22	1.498 (6)
C9—H9	0.98	C21—H21A	0.96
C10—H10	0.96	C21—H21B	0.95
C11—C12	1.548 (4)	C21—H21C	1.00
C11—H11A	0.96	C22—H22A	0.95
C11—H11B	0.96	C22—H22B	0.98
C12—C13	1.527 (5)	C22—H22C	0.97
C12—C14	1.536 (4)
C5—S1—C11	103.1 (1)	C12—C14—H14C	112
C15—O2—C20	107.1 (2)	H14A—C14—H14B	106
C16—O3—C20	109.8 (2)	H14A—C14—H14C	112
C19—O4—H4	107 (2)	H14B—C14—H14C	105
S1—C5—C6	123.0 (2)	O2—C15—C12	109.4 (2)
S1—C5—C10	118.5 (2)	O2—C15—C16	101.5 (2)
C6—C5—C10	118.5 (3)	O2—C15—H15	110
C5—C6—C7	119.8 (3)	C12—C15—C16	117.1 (2)
C5—C6—H6	120	C12—C15—H15	109
C7—C6—H6	121	C16—C15—H15	109
C6—C7—C8	121.7 (3)	O3—C16—C15	102.7 (2)
C6—C7—H7	120	O3—C16—C17	110.1 (2)
C8—C7—H7	118	O3—C16—H16	111
C7—C8—C9	119.9 (3)	C15—C16—C17	114.8 (2)
C7—C8—H8	118	C15—C16—H16	110
C9—C8—H8	122	C17—C16—H16	108
C8—C9—C10	120.8 (4)	C16—C17—C18	177.7 (3)
C8—C9—H9	120	C17—C18—C19	178.9 (3)
C10—C9—H9	119	O4—C19—C18	111.4 (3)
C5—C10—C9	119.3 (3)	O4—C19—H19A	114
C5—C10—H10	120	O4—C19—H19B	109
C9—C10—H10	120	C18—C19—H19A	109
S1—C11—C12	113.3 (2)	C18—C19—H19B	106
S1—C11—H11A	110	H19A—C19—H19B	108
S1—C11—H11B	110	O2—C20—O3	105.3 (2)
C12—C11—H11A	107	O2—C20—C21	109.6 (3)
C12—C11—H11B	108	O2—C20—C22	111.2 (2)
H11A—C11—H11B	109	O3—C20—C21	109.2 (2)
C11—C12—C13	106.6 (2)	O3—C20—C22	109.3 (3)
C11—C12—C14	109.9 (2)	C21—C20—C22	111.9 (3)
C11—C12—C15	109.6 (2)	C20—C21—H21A	111
C13—C12—C14	110.9 (3)	C20—C21—H21B	112
C13—C12—C15	111.8 (2)	C20—C21—H21C	108
C14—C12—C15	108.0 (3)	H21A—C21—H21B	111
C12—C13—H13A	112	H21A—C21—H21C	106
C12—C13—H13B	109	H21B—C21—H21C	107
C12—C13—H13C	111	C20—C22—H22A	113
H13A—C13—H13B	107	C20—C22—H22B	109
H13A—C13—H13C	111	C20—C22—H22C	110
H13B—C13—H13C	106	H22A—C22—H22B	109
C12—C14—H14A	112	H22A—C22—H22C	110
C12—C14—H14B	109	H22B—C22—H22C	107

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O4—H4···O3^i	0.98 (3)	1.86 (3)	2.816 (3)	164 (3)

Symmetry code: (i) x−1/2, −y+1/2, −z.