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Home , Oxindole, Spirotryprostatin B

Z. Kristallogr. NCS 225 (2010) 355-356 / DOI 10.1524/ncrs.2010.0155 355 © by Oldenbourg Wissenschaftsverlag, München

Crystal structureof2-spiro-3'-(2-)-3-benzoyl-4-phenyl-5- hydroxymethylpyrrolidine, C25H22N2O3

Yan-Qing MiaoI,Yan MengII,Qun-Zheng ZhangIII and Gang Chen*,III

I Xi'an Medical University, Department of Pharmacy, Hanguang Round No. 137, Xi’an 710021, Shannxi, P. R. China II Chang’an University, School of Environmental Engineering, South Second Cycle Road 368, Xi’an 710064, Shannxi, P. R. China III Xi’an Shiyou University, College of Chemistry and Chemical Engineering, Dianzi’er Road No.1 8, Xi’an 710065, Shannxi, P. R. China

Received March 25, 2010, accepted and available on-line April 22, 2010; CCDC no. 1267/2990

arylidene-1-tetralone and arylidenemalononitrile derivatives, have been efficiently used as trapping dipolarophiles [4-6]. Al- most all these reactions are in good yield and high regio- and ste- reo-selectivity. For aextended research of the regio-chemistry in 1,3-dipolar cycloaddition reaction of spiro[pyrrolidine-2,3'- oxindoline] compounds, L-serine was introduced in 1,3-dipolar cycloaddition reaction to synthesis the title compound. By the NMR and X-ray single crystal analysis, we can find the regio- slectivity and stereoselectivity of this reaction are same as the re- ported for 1,3-dipolar cycloaddition reactions between , other amino acid and chalcone. In the title crystal structure, molecules are interconnected by intermolecular hydrogen bonds N1–H1N···O3, N2–H2N···O1 and O3–H1O···N2, and form aone-dimensional arrangement. There are no intramolecular hydrogen bonds. Although the con- jugated system, isatin, was broken by the 1,3-dipolar cyclo- addition reaction, the -2-one moiety is still nearly planar Abstract with the C2–C8–C7–N1 torsion angle of –0.7(2)°.The newly C25H22N2O3,monoclinic, P21/n (no. 14), a =14.323(1) Å, constructed pyrrolidine displays atypical envelope conformation b =7.9521(6) Å, c =18.518(2) Å, b =94.248(2)°, with the relative configuration of 2S,3S,4S,5R,which consists 3 2 V =2103.4 Å , Z =4,Rgt(F) =0.046, wRref(F ) =0.121, with that of the product from the 1,3-dipolar cycloaddition reac- T =293 K. tion of isatin, L- and chalcone [6].

Source of material Table 1. Data collection and handling. Amixture of the isatin (0.147 g, 1mmol), L-serine (0.105 g, 1 mmol) and chalcone (0.250 g, 1.2 mmol) in methanol (20 mL) Crystal: colorless block, size 0.21 × 0.27 × 0.36 mm was stirred under reflux for 4hours. After completion of the reac- Wavelength: Mo Ka radiation (0.71073 Å) tion, it was evaporated to dryness, followed by chromatography m:0.83 cm−1 to the pure title compound (yield, 0.305 g, 84.2 %). 1H-NMR, Diffractometer, scan mode: Bruker SMART CCD, j/w 2q :56.44° 13C-NMR and EI-MS data are available in the CIF. max N(hkl)measured, N(hkl)unique:11761, 4993 Criterion for Iobs, N(hkl)gt: Iobs >2s(Iobs),3054 Experimental details N(param)refined:283 Hydrogen atoms bonded to atoms were located in adif- Programs: SHELXS-97, SHELXL-97, SHELXTL [7] ference Fourier map and refined isotropically without restraints.

Hydrogen atoms bonded to carbon atoms were positioned geo- 2 metrically and allowed to ride on their parent atoms with d(C—H) Table 2. Atomic coordinates and displacement parameters (in Å ). =0.93 Å and Uiso(H) =1.2 Ueq(C). Atom Site xyzUiso

Discussion H(2N) 4e 1.027(1) 0.769(2) −0.0144(9) 0.053(5) Spiro[pyrrolidine-2,3'-oxindole] ring system is astructural fea- H(1N) 4e 1.101(1) 1.227(2) −0.081(1) 0.061(6) ture found in awide variety of oxindole alkaloids, such as H(1O) 4e 0.941(1) 0.469(3) 0.065(1) 0.071(6) horsfiline 1[1] and [2], which have been re- H(10) 4e 1.2257 0.5498 0.0330 0.043 ported to behave as aldose reductase, poliovirus, and rhinovirus H(11) 4e 1.1067 0.7823 0.0987 0.043 H(12A) 4e 1.0793 0.4357 0.0661 0.050 3C-proteinase inhibitors [3]. The 1,3-dipolar cycloaddition reac- H(12B) 4e 1.0842 0.5131 0.1443 0.050 tion has also been employed for the construction of spiro- H(9) 4e 1.2666 0.8965 0.0452 0.043 [pyrrolidine-2,3'-oxindoline] derivatives. derivatives, H(3) 4e 1.1849 0.6240 −0.1501 0.057 such as chalcone, acrylate, maleimide, maleic anhydride 2- H(6) 4e 1.1213 1.1755 −0.2246 0.064 ______*Correspondence author (e-mail: [email protected]) 356 C25H22N2O3

Table 2. Continued. Table 2. Continued.

Atom Site xyzUiso Atom Site xyzUiso

H(25) 4e 1.3418 0.4171 0.1065 0.060 H(18) 4e 1.4219 1.3017 −0.0587 0.083 H(21) 4e 1.2347 0.8405 0.1811 0.071 H(17) 4e 1.5277 1.2305 −0.1402 0.093 H(4) 4e 1.1781 0.6955 −0.2719 0.069 H(23) 4e 1.4230 0.5790 0.3052 0.083 H(19) 4e 1.3304 1.0959 −0.0104 0.067 H(15) 4e 1.4543 0.7480 −0.1271 0.082 H(24) 4e 1.4323 0.3870 0.2138 0.077 H(22) 4e 1.3232 0.8034 0.2894 0.087 H(5) 4e 1.1476 0.9667 −0.3084 0.073 H(16) 4e 1.5427 0.9568 −0.1754 0.102

Table 3. Atomic coordinates and displacement parameters (in Å2).

Atom Site xyzU11 U22 U33 U12 U13 U23

O(3) 4e 0.96528(7) 0.5599(1) 0.08725(7) 0.0359(6) 0.0326(6) 0.0661(8) −0.0024(5) 0.0088(5) 0.0010(6) N(2) 4e 1.08575(8) 0.7284(2) −0.00854(7) 0.0302(7) 0.0324(7) 0.0461(8) −0.0002(5) 0.0015(5) 0.0037(6) C(1) 4e 1.1258(1) 1.0344(2) −0.01593(9) 0.0330(8) 0.0320(8) 0.049(1) 0.0006(6) 0.0044(7) 0.0015(8) N(1) 4e 1.12084(9) 1.1230(2) −0.07811(8) 0.0473(8) 0.0311(7) 0.0547(9) 0.0039(6) 0.0055(6) 0.0059(7) O(1) 4e 1.10804(8) 1.0873(1) 0.04356(6) 0.0664(8) 0.0394(7) 0.0519(8) 0.0081(5) 0.0119(6) −0.0049(6) C(10) 4e 1.21971(9) 0.6533(2) 0.06099(8) 0.0331(8) 0.0320(8) 0.0417(9) −0.0005(6) 0.0029(6) −0.0021(7) O(2) 4e 1.34642(8) 0.6143(2) −0.04577(7) 0.0651(8) 0.0458(7) 0.087(1) 0.0091(6) 0.0316(7) −0.0015(7) C(20) 4e 1.27829(9) 0.6332(2) 0.13149(8) 0.0317(8) 0.0405(9) 0.0427(9) −0.0039(6) 0.0041(6) 0.0023(7) C(11) 4e 1.11542(9) 0.6855(2) 0.06716(8) 0.0335(8) 0.0310(8) 0.0427(9) −0.0005(6) 0.0029(6) 0.0003(7) C(8) 4e 1.15688(9) 0.8571(2) −0.11423(8) 0.0319(8) 0.0392(9) 0.0443(9) −0.0015(6) 0.0043(6) −0.0006(8) C(7) 4e 1.1370(1) 1.0208(2) −0.13776(9) 0.0337(8) 0.0411(9) 0.047(1) −0.0022(6) 0.0036(7) 0.0041(8) C(13) 4e 1.3282(1) 0.7602(2) −0.03295(9) 0.0332(8) 0.047(1) 0.049(1) 0.0022(7) 0.0030(7) 0.0012(8) C(14) 4e 1.3829(1) 0.9001(2) −0.06312(9) 0.0344(8) 0.055(1) 0.046(1) −0.0051(7) 0.0002(7) 0.0085(8) C(2) 4e 1.15475(9) 0.8510(2) −0.03304(8) 0.0322(8) 0.0303(8) 0.0425(9) 0.0006(6) 0.0050(6) 0.0015(7) C(12) 4e 1.0640(1) 0.5340(2) 0.09392(9) 0.0363(8) 0.0369(9) 0.051(1) −0.0017(6) 0.0007(7) 0.0054(8) C(9) 4e 1.24783(9) 0.8018(2) 0.01352(8) 0.0328(7) 0.0315(8) 0.0434(9) −0.0020(6) 0.0029(6) −0.0020(7) C(3) 4e 1.1721(1) 0.7340(2) −0.16463(9) 0.0431(9) 0.049(1) 0.050(1) 0.0011(7) 0.0048(7) −0.0042(8) C(6) 4e 1.1337(1) 1.0655(2) −0.2098(1) 0.047(1) 0.059(1) 0.055(1) −0.0029(8) 0.0031(8) 0.016(1) C(25) 4e 1.3380(1) 0.4970(2) 0.1428(1) 0.044(1) 0.052(1) 0.053(1) 0.0029(8) 0.0019(8) 0.0073(9) C(21) 4e 1.2740(1) 0.7477(2) 0.1872(1) 0.048(1) 0.068(1) 0.061(1) 0.0045(9) −0.0021(8) −0.016(1) C(4) 4e 1.1681(1) 0.7775(3) −0.2375(1) 0.049(1) 0.075(1) 0.048(1) 0.0006(9) 0.0056(8) −0.013(1) C(19) 4e 1.3735(1) 1.0665(2) −0.0434(1) 0.048(1) 0.052(1) 0.068(1) −0.0064(8) 0.0041(8) 0.011(1) C(24) 4e 1.3920(1) 0.4783(3) 0.2075(1) 0.050(1) 0.076(1) 0.066(1) 0.0074(9) −0.0040(9) 0.021(1) C(5) 4e 1.1495(1) 0.9403(3) −0.2594(1) 0.051(1) 0.086(2) 0.044(1) −0.005(1) 0.0039(8) 0.006(1) C(18) 4e 1.4282(1) 1.1901(3) −0.0724(1) 0.064(1) 0.059(1) 0.083(2) −0.015(1) −0.005(1) 0.020(1) C(17) 4e 1.4909(1) 1.1477(3) −0.1210(1) 0.060(1) 0.096(2) 0.075(2) −0.027(1) −0.000(1) 0.032(1) C(23) 4e 1.3867(1) 0.5923(3) 0.2619(1) 0.047(1) 0.111(2) 0.049(1) −0.009(1) −0.0043(8) 0.013(1) C(15) 4e 1.4471(1) 0.8592(3) −0.1130(1) 0.059(1) 0.081(1) 0.067(1) −0.009(1) 0.021(1) −0.001(1) C(22) 4e 1.3277(1) 0.7259(3) 0.2522(1) 0.058(1) 0.105(2) 0.054(1) −0.008(1) 0.001(1) −0.024(1) C(16) 4e 1.5002(2) 0.9843(4) −0.1417(1) 0.071(2) 0.111(2) 0.077(2) −0.021(1) 0.029(1) 0.008(2)

Acknowledgments. This work was supported financially by the grants from Scientific Research Foundation for PhD of Xi'an Shiyou University (grant no. Z08008) and the Scientific Research Plan Projects of Shannxi Education De- partment (grant nos. 08JK413, 09JK702).

References

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