Crystal structure of (2/?,35,4S)-iV,3-0-dibenzyl-2-butyl-3,4-dihydroxy·

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Zeitschrift fur Kristallographie - New Crystal Structures 212, 203-204

© by R. Oldenbourg Verlag, München 1997

203

Crystal structure of (2/?,35,4S)-iV,3-0-dibenzyl-2-butyl-3,4-dihydroxy·

pyrrolidine,

C 2 2 H 2 9 N O 2

S. Henkel, O. Schwardt and V. Jäger

Universität Stuttgart. Institut für Organische Chemie, Pfaffenwaldring 55, D-70569 Stuttgart, Germany

Received August 7, 1996, CSD-No. 402588

Source of material: The title compound (see ref. 1) was prepared by Mitsunobu cyclization of (2S,3S,4/?)-3-0-benzyl-4-benzyl- amino-1,2,3-octantriol (see refs. 1,2) with triphenylphosphine and diethyl azodicarboxylate in pyridine. The crude product was puri- fied by silica gel chromatography with petroleum ether/diethyl ether 3:7 as eluent. After crystallization from heptane/ether the pyrrolidine was isolated in 76 % yield as colorless needles with mp 341-342 K.

The title compound belongs to a series of franj-dihydroxypyrro- lidines such as anisomycin, a known antibiotic which was recently found to have strong anti-tumor activities (see ref. 3).

C 2 2 H 2 9 N O 2 , monoclinic, P\2\\ (No. 4), a =12.004(3) Â,

b =7.301(2) Â, c =12.663(3) À, β =112.96(2)°, V=1021.9Â3, Z=2, R(F) =0.057, Ry/F2) =0.123.

Table 1. Parameters used for the X-ray data collection

Crystal: colorless needles, size 0.2 χ 0.25 χ 1.5 mm Wavelength: Mo Ka radiation (0.71073 λ )

μ: 0.70 cm"1

Diffractometer: Nicolet P3

Scan mode: Wyckoff

Τ measurement' ^{293 Κ}

2θπηχ: 50°

N(A¿/)umfu<: 1915 Criterion for l⁰: Io >2 σ(/0)

N(param)rcfme<f. 231

Programs: SHELXS-86, SHELXL-93

Table 2. Final atomic coordinates and displacement parameters (in A²)

Atom Site χ y ζ i/i»

2a 2a 2a 2a

H(2) H(3) H(4) H(4A)

H(5A) 2a H(5B) 2a H(6A) 2a H(6B) 2a H(7A) 2a H(7B)

H(8A) H(8B)

H(9A) 2a

H(9B) 2a

H(9C) 2a

H(11A) 2a H(11B) 2a H(13)

2a

2a 2a

H(14) H(15) H(16) H(17)

2a 2a 2a 2a 2a

H(18A) la H(18B) 2a H(20) H(21) H(22) H(23) H(24)

2a 2a 2a 2a 2a

0.7270(4) 0.7825(4) 0.5510(4) 0.576(4) 0.4504(4) 0.5715(4) 0.6794(5) 0.6626(5) 0.8846(6) 0.8675(6) 0.8616(9) 0.7868(9) 0.943(2)

1.020(2) 0.944(2) 0.7162(4) 0.8467(4) 0.8574(5) 0.9301(6) 0.9365(5) 0.8732(5) 0.8045(4) 0.4190(4) 0.5201(4) 0.4396(5) 0.5219(6) 0.6924(7) 0.7814(6) 0.7010(5)

0.3324(7) 0.2449(6) 0.2820(6) 0.002(7) 0.1532(6) 0.0821(6) 0.6704(7) 0.6471(7) 0.604(1) 0.583(1) 0.907(1) 0.902(1) 1.047(2) 0.877(2) 0.872(2) 0.3447(7) 0.3223(7) 0.422(1) 0.660(2) 0.952(1) 1.003(1) 0.7649(7) 0.3422(8) 0.4828(8) 0.0244(9) -0.193(1) -0.120(2) 0.162(2) 0.374(1)

0.7780(4) 0.6406(3) 0.4702(3) 0.449(4) 0.5730(3) 0.6704(3) 0.6621(4) 0.7779(4) 0.7555(6) 0.8716(6) 0.7513(9) 0.8278(9) 0.900(1) 0.895(1) 0.972(1) 0.4028(4) 0.4986(4) 0.2963(5) 0.2228(6) 0.2915(6) 0.4387(6) 0.5161(5) 0.7346(4) 0.8017(4) 0.7929(4) 0.9359(5) 1.0939(6) 1.1081(6) 0.9654(4)

0.074 0.070 0.070 0.07(2) 0.072 0.072 0.097 0.097 0.146 0.146 0.229 0.229 0.445 0.445 0.445 0.086 0.086

0.121

0.146 0.134 0.123 0.091 0.087 0.087 0.103 0.131 0.152 0.149 0.114

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204

(2Ä,35,45)-Ar,3-0-dibenzyl-2-butyl-3,4-dihydroxy-pyrrolidine

Table 3. Final atomic coordinates and displacement parameters (in Â²)

Atom Site X _y ζ l/ii ^Un C/33 Ul2 U,3 Un

N(l) 2a 0.5513(3) 0.3574(5) 0.6736(3) 0.060(2) 0.068(3) 0.056(2) 0.003(2) 0.021(2) -0.003(2) C(2) 2a 0.6810(4) 0.4020(7) 0.7084(4) 0.059(3) 0.069(3) 0.051(2) 0.000(2) 0.015(2) 0.001(2) C(3) 2a 0.7115(4) 0.3249(6) 0.6089(3) 0.051(2) 0.057(3) 0.063(2) 0.001(2) 0.019(2) -0.001(2) C(4) 2a 0.6023(4) 0.2107(6) 0.5371(3) 0.060(2) 0.058(3) 0.056(2) 0.000(2) 0.022(2) -0.007(2) 0(4) 2a 0.6384(3) 0.0475(5) 0.4998(3) 0.068(2) 0.070(2) 0.086(2) -0.004(2) 0.031(2) -0.022(2) C(5) 2a 0.5353(4) 0.1802(6) 0.6162(3) 0.059(2) 0.061(3) 0.059(2) -0.006(2) 0.020(2) -0.002(2) C(6) 2a 0.7079(5) 0.6037(7) 0.7340(4) 0.104(4) 0.076(4) 0.076(3) -0.017(3) 0.048(3) -0.020(3) C(7) 2a 0.8384(6) 0.647(1) 0.7987(6) 0.134(5) 0.108(5) 0.093(4) -0.056(5) 0.011(4) -0.015(4) C(8) 2a 0.8588(9) 0.854(1) 0.8205(9) 0.190(9) 0.17(1) 0.158(8) -0.103(9) 0.008(7) -0.023(7)

C(9) 2a 0.946(2) 0.916(2) 0.902(1) 0.41(2) 0.22(2) 0.19(1) -0.10(2) 0.04(1) -0.05(1)

0(10) 2a 0.7376(2) 0.4702(4) 0.5476(2) 0.067(2) 0.060(2) 0.073(2) -0.002(2) 0.036(2) -0.005(2) C ( l l ) 2a 0.7805(4) 0.4077(7) 0.4639(4) 0.073(3) 0.072(3) 0.072(3) -0.002(3) 0.031(2) -0.012(3) C(12) 2a 0.8231(4) 0.5689(7) 0.4157(4) 0.045(2) 0.075(3) 0.066(3) 0.003(2) 0.021(2) 0.003(3) C(13) 2a 0.8611(5) 0.540(1) 0.3262(5) 0.119(4) 0.108(5) 0.096(4) 0.011(4) 0.064(4) 0.000(4) C(14) 2a 0.9039(6) 0.682(2) 0.2817(6) 0.122(5) 0.156(8) 0.112(5) 0.008(6) 0.073(4) 0.027(6) C(15) 2a 0.9084(5) 0.856(1) 0.3224(6) 0.083(4) 0.130(7) 0.123(5) 0.002(5) 0.042(4) 0.043(5) C(16) 2a 0.8707(5) 0.885(1) 0.4098(6) 0.083(4) 0.096(4) 0.132(5) -0.009(4) 0.044(4) 0.010(4) C(17) 2a 0.8290(4) 0.7418(7) 0.4561(5) 0.072(3) 0.071(3) 0.095(4) -0.005(3) 0.042(3) -0.002(3) C(18) ^2a 03059(4) 0.3614(8) 0.7679(4) 0.073(3) 0.085(4) 0.065(3) 0.007(3) 0.034(2) -0.002(3) C(19) 2a 0.5609(4) 0.2237(8) 0.8622(4) 0.070(3) 0.103(4) 0.060(3) -0.006(3) 0.034(2) -0.006(3) C(20) 2a 0.5093(5) 0.0530(9) 0.8564(4) 0.081(3) 0.117(5) 0.066(3) 0.000(4) 0.035(3) 0.011(4) C(21) 2a 0.5579(6) -0.078(1) 0.9423(5) 0.124(5) 0.129(6) 0.092(4) -0.009(4) 0.061(4) 0.024(4) C(22) 2a 0.6591(7) -0.035(2) 1.0355(6) 0.114(6) 0.185(9) 0.084(4) 0.015(6) 0.043(4) 0.038(5) C(23) 2a 0.7123(6) 0.134(2) 1.0441(6) 0.092(4) 0.201(9) 0.069(4) -0.007(5) 0.021(3) 0.024(5) C(24) 2a 0.6637(5) 0.260(1) 0.9585(4) 0.090(4) 0.134(5) 0.062(3) -0.016(4) 0.029(3) -0.007(3)

References

1. Veith, U.; Schwardt, O.; Jäger, V: Concise synthesis of deacetylaniso- mycin and 2-substituted analogues from N,2-0-dibenzyl-L-threose imine. Synlett. In print.

2. Veith, U.: Stereoselektiver Aufbau von Aminodiolen und -triolen aus optisch aktiven Aldehyden - Synthese enantiomerenreiner, stickstoffhal- tiger Natur- und Wirkstoffe. Dissertation, University of Stuttgart, Ger- many 1995.

3. Veith, U.; Leurs, S.; Jäger, V.: Auxiliary-controlled diastereoselection by N-{ 1 -phenylethy 1) in Grignard additions to 2-0-benzyl-glyceraldehyde

¡mines. J. Chem. Soc. Chem. Commun. (19%) 329-330.

4. Hosoya, Y.; Kameyama, T.; Naganawa, H.; Okami, Y.; Takeuchi, T.:

Anisomycin and new congeners active against human tumor cell lines. J.

AntibioL 46 (1993) 1300-1302.

5. Sheldrick, G. M.: SHELX-86. Program for the solution of crystal structures. University of Göttingen, Germany 1986.

6. Sheldrick, G. M.: SHELXL-93, a program for refining crystal structures.

University of Göttingen, Germany 1993.