C32H51NO3, Mr = 497·7, orthorhombic, P212121, a = 7·577 (2), b = 10·510 (2), c = 35·399 (7) Å, V = 2819 (1) Å3, Z = 4, Dx = 1·173 g cm-3, λ (Mo Kα) = 0·71073 Å, μ = 0·69 cm-1, F(000) = 1096, T = 153 K, R = 0·0497 for 2235 observed reflections. The compound investigated is found to be a (22S)-epimer

Alexanyan, Mikael S.

Kamernitzky, Alexey V.

Lindeman, Sergey V.

Reshetova, Irina G.

Struchkov, Yuri T.

Thaper, Rajesh Kumar

English

epublications@Marquette

Marquette Universitye-Publications@MarquetteChemistry Faculty Research and Publications Chemistry, Department of1-1-1992Structure of (22S)-3β-Acetoxy-20-(3-isopropylisoxazolin-5-yl)-4,4,14 α-trimethylpregn-8(9)-eneSergey V. LindemanMarquette University, sergey.lindeman@marquette.eduMikael S. AlexanyanInstitute of Organoelement CompoundsYuri T. StruchkovInstitute of Organoelement CompoundsRajesh Kumar ThaperZelinsky Institute of Organic ChemistryIrina G. ReshetovaZelinsky Institute of Organic ChemistrySee next page for additional authorsPublished version. Acta Crystallographica Section C, Vol. 48 (1992): 290-292. DOI. © InternationalUnion of Crystallography 1992. Used with permission.AuthorsSergey V. Lindeman, Mikael S. Alexanyan, Yuri T. Struchkov, Rajesh Kumar Thaper, Irina G. Reshetova, andAlexey V. KamernitzkyActa Cryst. (1992). C48, 290--292 Structure of (22S)-3p-Acetoxy-20-(3-isopropylisoxazolin-5-yl)-4,4,14a-trimethylpregn-8(9)-ene BY SERGEY V. LINDEMAN,* MIKAEL S . .ALEXANYAN AND YURI T. STRUCHKOV Nesmeyanov Institute of Organoelement Compounds, Academy of Sciences of the USSR, 28 Vavilov Str., Moscow B-334, USSR AND RA.lEsH KUMAR l'HAPER, IRINA G. RESHETOVA AND ALEXEY v. KAMERNITZKY Zelinsky Institute of Organic Chemistry, Academy of Sciences of the USSR, 47 Leninskij Prosp., Moscow B-334, USSR (Received 11 December 1990; accepted 25 June 1991) Abstract. C32H 51N03, Mr = 497·7, orthorhombic, P21212b a= 7·577 (2), b = 10·510 (2), c = 35·399 (7) A, V = 2819 (1) A3, z = 4, Dx = 1·173 g cm- 3, A(Mo Ka) = 0·71073 A, JL = 0·69 cm- 1, F(OOO) = 1096, T= 153 K, R = 0·0497 for 2235 observed reflections. The compound investi-gated is found to be a (22S)-epimer. Introduction. Steroids having a lanostane skeleton and oxygen function in their side chain at C22 exhibit some useful biological properties (Kamernitzky & Reshetova, 1977). Isolation of such compounds from natural products and their * Author to whom correspondence should be addressed. 0108-2701/92/020290-03$03.00 synthesis may be of considerable interest. We have synthesized two isomers [(22R) and (liS)] of 3{3-acetoxy-20-(3-isopropylisoxazolin-5-yl)-4,4, 14a-tri-methylpregn-8(9)-ene (1). Biological activity of such steroid derivatives depends on the configuration of the C22 centre. Therefore the determination of chi-rality at the C22 atom in one epimer is of primary importance especially taking into account that further transformations proceed without inversion at the C22 atom. Experimental. The title compound (1) was prepared from 3 {3 -acetoxy-25,26,27 -trinorlanosta-8,22-diene (Poyser, Hirtzbach & Ourisson, 1974; Akhrem, Khripach, Litvinovskaya & Baranovsky, 1989) via © 1992 International Union of Crystallography SERGEY V. LINDEMAN et a/. 291 Table I. Atomic coordinates ( x 104) and equivalent isotropic displacement coefficients (A 2 x 1 03) Ueq is defined as one third of the trace of the orthogonalized uij tensor. Cl C2 C3 C4 cs C6 C7 C8 C9 CIO Cll Cl2 Cl3 Cl4 CIS Cl6 Cl7 CIS Cl9 C20 C21 C22 C23 C24 C25 C26 C27 C2S C29 C30 C41 C42 03 022 028 N24 X -4261 (6) -3941 (6) -2270 (6) -602 (6) -1013 (5) 563 (5) 269 (5) -1607 (5) -2964 (5) -2737 (5) -4S54 (5) -5133 (5) -3518 (5) -1910 (5) -446 (5) -1400 (5) -3431 (5) -3232 (6) -2675 (7) -4464 (6) -6452 (6) -4096 (6) -5102 (6) - 63S6 (6) -· 7S7S (7) -S099 (7) -9581 (7) -2042 (6) -IS21 (7) -2141 (6) sso (7) 54 (7) -2013 (4) -4629 (4) -2253 (6) -6110 (5) y - S367 (5) -8145 (S) - SS02 (4) - S423 (5) -8536 (4) -SISO (5) -SS54 (4) - S453 (4) -S232 (4) -7SS3 (4) -8180 (4) -8417(4) -8038 (4) -8785(4) -8440 (4) -8454 (5) -S446 (4) -6584 (4) -6409 (4) -7686 (4) -7632 (5) -8276 (4) -7703 (5) -8751 (4) - S668 (5) -9S84 (5) -8324 (6) - 93S7 (4) -8782 (5) -10244 (4) -9396 (6) -7110 (5) - S465 (3) -9612 (3) -10468 (3) -9778 (4) z -1423 (I) -1001 (I) -875 (I) -1092 (I) -1524 (I) -1770 (I) -2175 (I) -231S (I) -208S (I) -1667 (I) -2236 (I) -2662 (I) -2890 (I) -2723 (I) -3008 (I) -3395 (I) -3313 (I) -2859 (I) -165S (I) -3613 (I) -3531 (I) -4000 (I) -4336 (I) -4418 (I) -4700 (I) -4924 (2) -4490 (2) -21S (I) 172 (I) -2741 (I) -991 (I) -977 (I) -47S (I) -3993 (I) -273 (I) -4240 (I) Perspective view of compound (I). Ucq 29 (I) 33 (I) 30 (I) 32 (I) 25 (I) 33 (I) 28 (I) 20 (I) 21 (I) 22 (I) 24 (I) 26 (I) 20 (I) 21 (I) 28 (I) 29 (I) 23 (I) 29 (I) 33 (I) 28 (I) 33 (I) 31 (I) 36 (I) 31 (I) 36 (2) 49 (2) 50 (2) 33 (I) 45 (2) 30 (I) 4S (2) 42 (2) 35 (I) 37 (I) 57 (I) 36 (I) 1 ,3-dipolar cycloaddition of isopropylnitrile oxide. Suitable crystals of the individual epimer (m.p. 522-523 K) were prepared by crystallization from EtOAc. The X-ray intensity data from a colourless 0· 30 x 0· 35 x 0·85 mm crystal were collected with an auto-mated Syntex P21 four-circle diffractometer at 153 K using graphite-monochromated Mo Ka radiation. The unit-cell parameters were determined on the basis of accurately measured positions of 24 reflec-tions in the 13 < () < 14° range. The intensities of 3733 reflections (0 s; h s; 9, 0 s; k s; 13, 0 s; Is; 46) were measured using 8/28 scans (background/peak time ratio 0·25) in the () range from 2·0 to 30·0° with a variable scan speed (3·0-30·0° min- 1 in w). The intensities of two standard reflections (measured every 98 reflections) did not show any significant changes [o(l) < 3%]. CIO Cl Cl C2 C2 C2 03 03 03 C3 C3 C41 C41 C42 C42 C4 CIO cs C6 C6 C7 C7 Cl4 Cl4 C2 C2 C2 C4 C4 C4 C6 C6 C6 cs C8 C8 Cll Cll Cll C8 CIO C9 Cll Cll CII C7 C7 C7 C9 Cl C2 C2 C3 C3 C3 C3 C3 C3 C4 C4 C4 C4 C4 C4 cs cs C6 C7 C7 cs C8 C8 cs Cl Cl Cl cs cs cs cs cs cs C9 C9 C9 C9 C9 C9 C9 C9 Cll Cl2 Cl2 Cl2 cs C8 C8 cs C2 C3 C3 C4 C4 C4 C4 C4 C4 cs cs cs cs cs cs C6 C6 C7 cs C8 C9 C9 C9 C9 CIO CIO CIO CIO CIO CIO CIO CIO CIO CIO CIO CIO CIO CIO CIO Cll Cll Cl2 Cl3 Cl3 Cl3 Cl4 Cl4 C14 Cl4 Table 2. Torsion angles CO) C3 - SS·S C4 56·5 03 176·2 cs - S0·2 C41 -167·0 C42 74·9 cs -169·2 C41 74·0 C42 -44·1 C6 -180·0 CIO 49·5 C6 -63·S CIO 165·6 C6 SS·S CIO -74·7 C7 168·1 C7 - S8·6 cs 34·5 C9 -9·6 Cl4 17S·2 CIO 8·5 Cll -17S·O CIO -179·7 Cll -6·1 cs 55·6 C9 173·9 Cl9 -6S·8 Cl - S2·8 C9 - 174·2 Cl9 69·1 Cl 176·0 C9 54·6 Cl9 -62·1 Cl -148·8 cs - 30·5 Cl9 91·S Cl 37-4 cs 155-6 Cl9 -82-4 Cl2 1·2 Cl2 175·1 Cl3 - 27·S Cl4 S5·S Cl7 168·7 CIS - 65·0 Cl3 -ISI·I CIS - 34·9 C30 84·8 Cl3 36·6 C9 CS Cl4 C9 C8 Cl4 Cl2 Cl3 Cl4 Cl2 Cl3 Cl4 Cl2 Cl3 Cl4 Cl7 Cl3 Cl4 Cl7 Cl3 Cl4 C17 Cl3 Cl4 CIS Cl3 Cl4 CIS Cl3 Cl4 CIS Cl3 Cl4 C8 Cl4 CIS Cl3 Cl4 CIS C30 Cl4 CIS Cl4 CIS Cl6 Cl2 Cl3 Cl7 Cl2 Cl3 Cl7 Cl4 Cl3 Cl7 Cl4 Cl3 Cl7 CIS Cl3 Cl7 CIS Cl3 Cl7 CIS Cl6 Cl7 CIS Cl6 Cl7 Cl3 Cl7 C20 Cl3 Cl7 C20 Cl6 Cl7 C20 Cl6 Cl7 C20 Cl7 C20 C22 Cl7 C20 C22 C21 C20 C22 C21 C20 C22 C20 C22 C23 022 C22 C23 C22 C23 C24 C22 C23 C24 C23 C24 C2S C23 C24 C25 N24 C24 C2S N24 C24 C25 C2 C3 03 C4 C3 03 C29 C28 03 028 C28 03 C20 C22 022 C23 C22 022 C23 C24 N24 C2S C24 N24 C22 022 N24 CIS C30 C8 CIS C30 C8 CIS C30 C8 CIS C30 Cl6 Cl6 Cl6 Cl7 Cl6 C20 Cl6 C20 Cl6 C20 Cl3 C20 C21 C22 C21 C22 C23 022 C23 022 C24 C24 C25 N24 C26 C27 C26 C27 C2S C2S C3 C3 N24 N24 022 022 C24 ISZ.S -87·5 -60·8 173-4 59·5 174·9 49·1 -64·8 SS·7 -67·1 179·0 -160·7 -39·1 79·6 14·7 -ISH 79·3 -39·4 -164·3 77·9 -47·0 15·7 14S·5 -S?-9 178·5 -17S·3 58·1 176·2 58·4 51·7 -66·1 -108·0 12·2 173·1 -9·2 139·6 -96·9 -37·9 85·5 116·9 -IIS·8 -177-7 0·7 112·8 -12·3 1·9 179·7 6·9 All calculations were performed with an IBM-PC/AT computer using SHELXTL-Plus (PC Version; Sheldrick, 1989). The intensities of 2235 independent observed [/ > 3u(/)] reflections correc-ted for Lorentz and polarization factors were used. The structure was solved using direct methods and refined by full-matrix least squares in anisotropic approximation for non-H atoms. H atoms were placed in calculated positions and refined isotropi-cally with a fixed Uiso = 0·08 A2• The final refinement of 289 parameters converged to R = 0·0497, w R = 0·0498 [w- 1 = u 2(F) + 99·000F2], S = 1·17, mean (..diu)= 0·170, 0·23 > 11p > - 0·19 e A - 3• Discussion. Atomic coordinates and equivalent iso-tropic thermal parameters are given in Table 1. * The * Lists of structure factors, anisotropic thermal parameters, full bond lengths and angles, and H-atom parameters have been deposited with the British Library Document Supply Centre as Supplementary Publication No. SUP 54394 (20 pp.). Copies may be obtained through The Technical Editor, International Union of Crystallography, 5 Abbey Square, Chester CHI 2HU, England. 292 molecular structure with atom numbering is shown in Fig. 1. Bond lengths and angles are unexceptional (Allen, Kennard, Watson, Brammer, Orpen & Taylor, 1987; Duax & Norton, 1975). The determination of absolute configuration of the C22 chiral centre, which turned out to be S, was based on the known chirality of the steroid framework. The main torsion angles, which characterize the molecular conformation, are given in Table 2. The steroid framework conformation coincides with a standard for .J8(9)-pregnanes (Duax & Norton, 1975), viz. a chair for the A ring, a 5a-sofa for the Bring, a 13{3-sofa for the C ring and a 14a-envelope for the Dring. The orientation of the side chain at C17, characterized by the torsion angle C16 C17 C20 C21 = -178·3°, may be considered as sterically least strained. The oxazoline ring is in fact planar. The orientation of the 3{3-acetoxy group Acta Cryst. (1992). C48, 292-295 [with the carbonyl 0 and H(C3) atoms disposed close to each other] is similar to that usually observed in most of the analogous steroid derivatives (Duax & Norton, 1975). References AKIIREM, A. A., KHRIPACH, v. A., LITVINOVSKAYA, R. P. & BARANOVSKY, A. V. (1989). Zh. Org. Khim. 25, 1901-1908. ALLEN, F. H., KENNARD, 0., WATSON, D. G., BRAMMER, L., 0RPEN, A. G. & TAYLOR, R. (1987). J. Chern. Soc. Perkin Trans. 2, S1-S19. DuAX, W. L. & NoRTON, D. A. (1975). Atlas of Steroid Structure, Vol. 1. New York: IFI/Plenum. KAMERNITZKY, A. V. & REsHETOVA, I. G. (1977). Khim. Prir. Soedin. pp. 156-186. POYSER, J. P., HIRTZBACH, F. R. & 0URISSON, G. (1974). Tetra-hedron, 30, 977-983. SHELDRICK, G. M. (1989). SHELXTL-Plus Structure Deter-mination Software Programs. PC Version. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. 

Structure of (22\u3cem\u3eS\u3c/em\u3e)-3\u3cem\u3eβ\u3c/em\u3e-Acetoxy-20-(3-isopropylisoxazolin-5-yl)-4,4,14 \u3cem\u3eα\u3c/em\u3e-trimethylpregn-8(9)-ene

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Structure of (22\u3cem\u3eS\u3c/em\u3e)-3\u3cem\u3eβ\u3c/em\u3e-Acetoxy-20-(3-isopropylisoxazolin-5-yl)-4,4,14 \u3cem\u3eα\u3c/em\u3e-trimethylpregn-8(9)-ene

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