ELECTROPHILIC SUBSTITUTION OF HYDROGEN IN BETULIN
137
3.06 t.d (1H, 19-H, J = 10.8, 5.5 Hz), 3.19 d.d (1H,
3-H, J = 11.2, 4.6 Hz), 3.40 d and 3.80 d (2H, 28-H,
2J = 11.2 Hz), 5.74 s (1H, =CHBr). 13C NMR spec-
trum, δC, ppm: 42.8 (C19), 60.54 (C28), 79.1 (C3), 100.1
(C29), 145.4 (C20).
29-Iodolup-20(29)-ene-3β,28-diyl diacetate (3f).
A small amount of vinyl isomers in a mixture with 2f.
1H NMR spectrum, δ, ppm: 5.74 s and 5.91 s
(=CHI, Z, E).
This study was performed under financial support
by the Russian Foundation for Basic Research
(project no. 16-03-01066-A). The authors thank Prof.
G.K. Fukin for performing X-ray analysis and inter-
preting the X-ray diffraction data. The analytical data
were obtained at the Joint Analytical Center (Razuvaev
Institute of Organometallic Chemistry, Russian
Academy of Sciences).
(E)-29-Bromolup-20(29)-ene-3β,28-diol (E-3c).
1H NMR spectrum, δ, ppm: 2.52 t.d (1H, 19-H, J =
10.6, 6.1 Hz), 3.19 d.d (1H, 3-H, J = 11.2, 4.6 Hz),
3.30 d and 3.79 d (2H, 28-H, 2J = 9.7 Hz), 5.90 s (1H,
=CHBr). 13C NMR spectrum, δC, ppm: 48.5 (C19),
60.65 (C28), 79.1 (C3), 101.1 (C29), 146.4 (C20).
30-Bromolup-20(29)-ene-3β,28-diyl diacetate
1
(2d). H NMR spectrum, δ, ppm: 2.04 s and 2.078 s
REFERENCES
[3H each, OC(O)CH3], 2.44 t.d (1H, 19-H, J = 11.2,
5.4 Hz), 3.99 m (2H, CH2Br, 2J = 11.0 Hz), 5.03 s and
5.13 s (2H, =CH2).
1. Lerman, B.N., Russ. Chem. Rew., 1995, vol. 64,
no. 1, p. 1.
(Z)-29-Bromolup-20(29)-ene-3β,28-diyl diacetate
(Z-3d). H NMR spectrum, δ, ppm: 2.04 s and 2.084 s
2. Bodrikov, I.V. and Smolyan, Z.S., Russ. Chem. Rev.,
1
1966, vol. 35, no. 5, p. 374.
[3H each, OC(O)CH3], 3.12 t.d (1H, 19-H, J = 11.0,
5.6 Hz), 5.75 s (1H, =CHBr).
3. Bodrikov, I.V., Borisova, N.V., Chiyanov, A.A.,
Kurskii, Yu.A., and Fukin, G.K., Russ. J. Org. Chem.,
2013, vol. 49, no. 1, p. 78.
4. Yemets, S.V., Shubina, T.E., and Krasutsky, P.A., Org.
Biomol. Chem., 2013, vol. 11, no. 17, p. 2891.
5. Bodrikov, I.V., Kurskii, Yu.A., Chiyanov, A.A.,
Borisova, N.V., and Subbotin, A.Yu., Dokl. Chem.,
2013, vol. 450, no. 2, p. 162.
(E)-29-Bromolup-20(29)-ene-3β,28-diyl diacetate
(E-3d). 1H NMR spectrum, δ, ppm: 2.04 s and 2.073 s
[3H each, OC(O)CH3], 2.57 t.d (1H, 19-H, J = 10.9,
5.7 Hz), 5.91 s (1H, =CHBr).
30-Iodolup-20(29)-ene-3β,28-diol (2e). 1H NMR
spectrum, δ, ppm: 0.68 m (1H, 5-H); 0.76 s, 0.82 s,
0.97 s, 0.99 s, and 1.03 s (3H each, CH3), 0.84–2.05 m
(1-H, 2-H, 6-H, 7-H, 9-H, 11-H, 12-H, 13-H, 15-H,
16-H, 18-H, 21-H, 22-H), 2.22–2.40 m (2H, 19-H,
21-H), 3.19 d.d (1H, 3-H, J = 11.1, 4.8 Hz), 3.33 d and
6. Hartwig, J.F. and Stanley, L.M., Acc. Chem. Res., 2010,
vol. 43, no. 12, p. 1463.
7. Liao, J., Guo, W., Zhang, Z., Tang, X., Wu, W., and
Jiang, H., J. Org. Chem., 2016, vol. 81, no. 3, p. 1304.
8. Zhang, Z.-Q., Zhang, B., Lu, X., Liu, J.-H., Lu, X.-Y.,
Xiao, B., and Fu, Y., Org. Lett., 2016, vol. 18, no. 5,
p. 952.
9. Chen, M. and Hartwig, J.F., Angew. Chem., Int. Ed.,
2016, vol. 128, no. 38, p. 11823.
10. Nitelet, A. and Evano, G., Org. Lett., 2016, vol. 18,
2
3.81 d (2H, 28-H, J = 10.8 Hz), 3.94 m (2H, CH2I,
2J = 9.3 Hz), 4.99 s and 5.17 s (2H, =CH2). 13C NMR
spectrum, δC, ppm: 11.9 br (C30), 14.9, 15.5, 16.1, 16.2,
28.1 (CH3), 18.4, 21.0, 26.8, 27.1, 27.4, 29.3, 33.2,
33.9, 34.4, 37.26, 37.33, 38.8, 39.0, 41.1, 42.8, 43.9 br
(C19), 47.7, 50.5, 50.7, 55.3, 60.4 (C28), 79.1 (C3),
112.1 (C29), 152.1 (C20).
no. 8, p. 1904.
11. Hamilton, J.Y., Sarlah, D., and Carreira, E.M., J. Am.
Chem. Soc., 2013, vol. 135, no. 3, p. 994.
12. Kuhl, N., Schröder, N., and Glorius, F., Org. Lett., 2013,
29-Iodolup-20(29)-ene-3β,28-diol (3e). A small
amount of vinyl isomers in a mixture with 2e. 1H NMR
spectrum, δ, ppm: 5.72 s and 5.90 s (=CHI, Z, E).
vol. 15, no. 15, p. 3860.
13. Bębenek, E., Kadela-Tomanek, M., Chrobak, E.,
Wietrzyk, J., Sadowska, J., and Boryczka, S., Med.
Chem. Res., 2016, vol. 26, no. 1, p. 1.
30-Iodolup-20(29)-ene-3β,28-diyl diacetate (2f).
1H NMR spectrum, δ, ppm: 0.78 m (1H, 5-H); 0.83 s,
0.84 s, 0.85 s, 0.98 s, and 1.04 s (3H each, CH3); 0.94–
1.88 m (1-H, 2-H, 6-H, 7-H, 9-H, 11-H, 12-H, 13-H,
15-H, 16-H, 18-H, 21-H, 22-H), 2.04 s and 2.08 s [3H,
OC(O)CH3], 2.27 m (1H, 21-H), 2.40 t.d (1H, 19-H,
14. Gorbunova, M.N., Krainova, G.F., Kisel’kov, D.M., and
Nebogatikov, V.O., Russ. J. Appl. Chem., 2016, vol. 89,
no. 3, p. 439.
15. Ortiz, A., Soumeillant, M., Savage, S.A., Strot-
man, N.A., Haley, M., Benkovics, T., Nye, J., Xu, Z.,
Tan, Y., Ayers, S., Gao, Q., and Kiau, S., J. Org. Chem.,
2017, vol. 82, no. 9, p. 4958.
2
J = 10.9, 5.3 Hz), 3.84 d and 4.87 d (2H, 28-H, J =
10.8 Hz), 3.93 m (2H, CH2I, 2J = 9.3 Hz), 4.46 m (1H,
3-H), 4.98 s and 5.18 s (2H, =CH2).
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 54 No. 1 2018