213
Z. Kristallogr. NCS 221 (2006) 213-214 / DOI 10.1524/ncrs.2006.0043
© by Oldenbourg Wissenschaftsverlag, München
Crystal structure of (3R,6S,4¢S)-2-benzyl-3-(2¢,2¢-dimethyl[1¢,3¢]dioxolan4¢-yl)-4-methoxy-6-phenyl-3,6-dihydro-2H-1,2-oxazine, C23H27NO4 M. A. Chowdhury, I. Brüdgam, H. Hartl and H.-U. Reißig* Freie Universität Berlin, Institut für Chemie und Biochemie, Takustr. 3, 14195 Berlin, Germany Received April 27, 2006, accepted and available on-line May 27, 2006; CCDC no. 1267/1774 Table 1. Data collection and handling. Crystal: Wavelength: m: Diffractometer, scan mode: 2qmax: N(hkl)measured, N(hkl)unique: Criterion for Iobs, N(hkl)gt: N(param)refined: Programs:
colorless prism, size 0.32 × 0.41 × 0.61 mm Mo Ka radiation (0.71073 Å) 0.86 cm−1 Bruker SMART CCD, j/w 61.14° 12242, 6002 Iobs > 2 s(Iobs), 5044 256 SHELXS-97 [3], SHELXL-97 [4], ORTEP-3 [5]
Table 2. Atomic coordinates and displacement parameters (in Å2).
Abstract C23H27NO4, monoclinic, P1211 (no. 4), a = 10.053(3) Å, b = 9.859(3) Å, c = 10.202(3) Å, b = 96.087(6)°, V = 1005.4 Å3, Z = 2, Rgt(F) = 0.054, wRref(F2) = 0.138, T = 173 K. Source of material The title compound was obtained by reaction of lithiated 1-methoxy-3-phenylallene generated in situ [1] with the complex of (Z)N-(1-deoxy-2,3-O-isopropylidene-D-glycero-1-ylidene)benzylamine N-oxide with diethylaluminum chloride analogously to the procedure described in [2], purified by column chromatography on silica gel and recrystallized from diethyl ether/hexane (m.p. 436-438 K). Discussion The crystal structure proves the configuration of the product at C11 and C8 revealing a trans-relationship of the two substituents and an anti-configuration of C11 with respect to C12. This result can be explained by an addition of (aS)-configured 1-lithio-1methoxy-3-phenylallene to the Si-face of the nitrone [2]. Bond distances and bond angles show normal values. The conformation of the 1,2-oxazine ring is a flat chair with substituents at C8 and C11 in equatorial positions. The H11C11C12H12 dihedral angle is 66°.
Atom
Site
x
y
z
Uiso
H(1) H(3) H(4) H(5) H(7A) H(7B) H(8) H(9) H(11) H(12) H(13A) H(13B) H(15A) H(15B) H(15C) H(16A) H(16C) H(16B) H(17A) H(17B) H(17C) H(19) H(20) H(21) H(2) H(22) H(23)
2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a
0.7595 0.8490 0.6935 0.5708 0.4824 0.6153 0.6989 0.6390 0.4726 0.2743 0.2796 0.4226 0.2769 0.1295 0.1497 0.0048 0.0701 0.0143 0.4704 0.5507 0.3956 0.8684 1.0892 1.2149 0.8800 1.1199 0.9010
0.6692 1.0013 1.1262 1.0237 0.7522 0.6801 1.0375 0.9541 0.6969 0.8291 1.0551 1.0521 0.9159 0.9790 0.8183 0.9896 0.9212 0.8280 0.9133 0.7729 0.7764 0.7478 0.7506 0.9504 0.7717 1.1479 1.1438
0.5842 0.3784 0.4821 0.6376 0.6851 0.7522 0.9653 1.1946 0.9267 0.9614 0.9486 0.8907 0.5349 0.5232 0.5349 0.7251 0.8590 0.7370 1.3089 1.3202 1.3425 1.1292 1.2275 1.2310 0.4281 1.1362 1.0314
0.040 0.052 0.057 0.048 0.029 0.029 0.023 0.025 0.023 0.024 0.029 0.029 0.054 0.054 0.054 0.055 0.055 0.055 0.047 0.047 0.047 0.030 0.037 0.036 0.036 0.037 0.030
Table 3. Atomic coordinates and displacement parameters (in Å2). Atom
Site
x
y
z
U11
U22
U33
O(1) O(2) O(3)
2a 2a 2a
0.7056(1) 0.4290(1) 0.2796(1)
0.8417(1) 0.7919(1) 0.8101(1)
0.9099(1) 1.1547(1) 0.7675(1)
0.0172(5) 0.0206(5) 0.0247(6)
0.0234(5) 0.0344(6) 0.0223(6)
0.0207(5) 0.0218(6) 0.0264(6)
_____________
* Correspondence author (e-mail:
[email protected])
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U12 0.0017(4) −0.0027(5) 0.0012(5)
U13 0.0003(4) 0.0049(4) −0.0061(5)
U23 −0.0043(4) 0.0038(5) −0.0027(5)
214
C23H27NO4
Table 3. Continued. Atom
Site
x
y
z
U11
U22
U33
O(4) N(1) C(1) C(2) C(3) C(4) C(5) C(6) C(7) C(8) C(9) C(10) C(11) C(12) C(13) C(14) C(15) C(16) C(17) C(18) C(19) C(20) C(21) C(22) C(23)
2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a 2a
0.2665(1) 0.5695(1) 0.7459(2) 0.8177(2) 0.7991(2) 0.7072(3) 0.6343(2) 0.6544(2) 0.5745(2) 0.7200(2) 0.6238(2) 0.5174(2) 0.4753(2) 0.3344(2) 0.3309(2) 0.1954(2) 0.1872(2) 0.0591(2) 0.4642(2) 0.8631(2) 0.9196(2) 1.0506(2) 1.1254(2) 1.0695(2) 0.9387(2)
1.0383(1) 0.8528(1) 0.7626(2) 0.8232(3) 0.9591(3) 1.0330(2) 0.9721(2) 0.8360(2) 0.7689(2) 0.9475(2) 0.9183(2) 0.8415(2) 0.7981(2) 0.8573(2) 1.0141(2) 0.9172(2) 0.9067(2) 0.9137(2) 0.8155(2) 0.9457(2) 0.8289(2) 0.8307(2) 0.9495(2) 1.0663(2) 1.0639(2)
0.7521(1) 0.8443(1) 0.5641(2) 0.4710(2) 0.4411(2) 0.5030(2) 0.5961(2) 0.6283(2) 0.7265(2) 1.0077(2) 1.1079(2) 1.0728(2) 0.9326(2) 0.8942(2) 0.8811(2) 0.7114(2) 0.5631(2) 0.7627(2) 1.2924(2) 1.0697(2) 1.1291(2) 1.1883(2) 1.1904(2) 1.1335(2) 1.0720(2)
0.0379(8) 0.0164(6) 0.0311(9) 0.0301(9) 0.043(1) 0.070(2) 0.052(1) 0.0257(8) 0.0263(8) 0.0190(7) 0.0187(7) 0.0168(6) 0.0186(7) 0.0163(7) 0.0236(8) 0.0240(8) 0.038(1) 0.0225(9) 0.0296(9) 0.0172(7) 0.0231(8) 0.0278(9) 0.0182(8) 0.0214(8) 0.0223(8)
0.0222(6) 0.0216(6) 0.044(1) 0.067(2) 0.065(2) 0.039(1) 0.034(1) 0.0306(8) 0.0242(7) 0.0185(7) 0.0237(7) 0.0193(6) 0.0190(6) 0.0209(7) 0.0199(7) 0.0250(8) 0.047(1) 0.054(1) 0.045(1) 0.0228(7) 0.0237(8) 0.0318(9) 0.040(1) 0.0308(8) 0.0228(7)
0.0322(7) 0.0178(6) 0.0237(9) 0.0267(9) 0.0227(9) 0.035(1) 0.036(1) 0.0171(7) 0.0218(8) 0.0204(7) 0.0199(7) 0.0201(7) 0.0206(7) 0.0225(7) 0.0286(8) 0.0234(8) 0.0229(9) 0.033(1) 0.0209(8) 0.0195(7) 0.0289(8) 0.0314(9) 0.0316(9) 0.040(1) 0.0302(8)
U12 −0.0011(5) −0.0002(5) 0.0053(8) 0.003(1) −0.020(1) −0.012(1) 0.0013(9) −0.0012(7) −0.0009(6) −0.0003(6) 0.0014(6) 0.0032(5) −0.0004(6) −0.0005(6) 0.0032(6) 0.0025(7) 0.0032(9) 0.0046(9) 0.0010(8) −0.0009(6) −0.0015(6) 0.0050(7) 0.0003(7) −0.0072(7) −0.0023(6)
U13 −0.0059(6) 0.0002(5) 0.0036(7) 0.0061(7) 0.0054(8) 0.014(1) 0.016(1) −0.0001(6) 0.0032(6) 0.0024(5) 0.0031(6) 0.0033(5) 0.0017(5) 0.0002(5) 0.0005(6) −0.0010(6) −0.0011(8) 0.0008(7) 0.0059(7) 0.0038(5) 0.0005(6) −0.0020(7) −0.0007(6) 0.0057(7) 0.0037(6)
U23 0.0040(5) −0.0018(5) −0.0035(8) −0.005(1) −0.0011(9) 0.0025(9) −0.0001(8) −0.0051(6) −0.0066(6) −0.0012(5) −0.0015(6) 0.0031(5) 0.0008(5) 0.0009(6) −0.0041(6) 0.0013(6) 0.0020(8) 0.0003(9) 0.0059(7) −0.0028(6) −0.0003(6) −0.0010(7) −0.0088(8) −0.0069(8) −0.0006(6)
Acknowledgments. Support of this work by the Alexander-von-Humboldt Foundation (Research Fellowship to M.A.C.), the Deutsche Forschungsgemeinschaft, the Fonds der Chemischen Industrie and the Schering AG is most gratefully acknowledged.
References 1. Chowdhury, M. A.; Reissig, H.-U.: Syntheses of Highly Substituted Furan and Pyrrole Derivatives by Additions of 3-Aryl-Substituted Lithiated 1Methoxyallenes Application to the Synthesis of Codonopsinine. Synlett (2006), manuscript submitted. 2. Helms, M.; Schade, W.; Pulz, R.; Watanabe, T.; Al-Harrasi, A.; Fiera, L.; Hlobilová, I.; Zahn, G.; Reißig, H.-U.: Stereodivergent Syntheses of Highly Substituted Enantiopure 4-Alkoxy-3,6-dihydro-2H-1,2-oxazines by Addition of Lithiated Alkoxyallenes to Carbohydrate-Derived Aldonitrones. Eur. J. Org. Chem. (2005) 1003-1019.
3. Sheldrick, G. M.: Phase Annealing in SHELX-90: Direct Methods for Larger Structures. Acta Crystallogr. A46 (1990) 467-473. 4. Sheldrick, G. M.: SHELXL-97. Program for the Refinement of Crystal Structures. University of Göttingen, Germany 1997. 5. Farrugia, L. J.: ORTEP-3 for Windows a version of ORTEP-III with a Graphical User Interface (GUI). J. Appl. Crystallogr. 30 (1997) 565.
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