1195
S. Ajay et al.
Paper
Synthesis
moved under reduced pressure to give a residue that was purified by
column chromatography (silica gel, EtOAc/hexane, 4:96) to give 9 (78
mg, 91%) as a pale yellow liquid; Rf = 0.6 (EtOAc/hexane, 1:9).
[α]D28 –1.9 (c 0.34, CHCl3).
References
(1) Sobin, B. A.; Tanner, F. W. J. Am. Chem. Soc. 1954, 76, 4053.
(2) (a) Ishida, S.; Yamada, O.; Futatsuya, F.; Ito, K.; Yamamoto, H.;
Munakata, K. Proceedings of the First Intersectional Congress of
IAMS; Vol. 3; Hasegawa, T., Ed.; Science Council of Japan: Tokyo,
1975, 641. (b) Hosoya, Y.; Kameyama, T.; Naganawa, H.; Okami,
Y.; Takeuchi, T. J. Antibiot. 1993, 46, 1300.
(3) Beereboom, J. J.; Butler, K.; Pennington, F. C.; Solomons, I. A.
J. Org. Chem. 1965, 30, 2334.
(4) Wong, C. M. Can. J. Chem. 1968, 46, 1101.
IR (neat): 3607, 2821, 2133, 1729, 1635, 1358, 1212, 817, 741 cm–1
.
1H NMR (500 MHz, CDCl3): δ = 7.67–7.69 (m, 2 H), 7.23–7.24 (m, 5 H),
7.10–7.12 (m, 2 H), 6.96–6.98 (m, 2 H), 6.75–6.77 (m, 2 H), 4.98 (m, 1
H), 4.49–4.52 (m, 1 H), 4.33–4.36 (m, 1 H), 4.18 (dd, J1 = 11.03 Hz, J2 =
3.40 Hz, 1 H), 4.08–4.12 (m, 1 H), 3.78–3.81 (m, 1 H), 3.72 (s, 3 H),
3.54–3.58 (m, 1 H), 2.65–2.66 (m, 2 H), 2.36 (s, 3 H), 2.00 (s, 3 H).
(5) Schaefer, J. P.; Wheatley, P. J. J. Org. Chem. 1968, 33, 166.
(6) (a) Jimenez, A.; Vazquez, D. In Antibiotics; Hahn, F. E., Ed.;
Springer: Berlin, 1979, 1–19. (b) Grollman, A. P. J. Biol. Chem.
1967, 242, 3226.
(7) Schwartdt, O.; Veith, U.; Gaspard, C.; Jager, V. Synthesis 1999,
1473.
13C NMR (100 MHz, CDCl3): δ = 171.2, 159.1, 145.4, 137.5, 133.1,
130.5, 130.3, 128.9, 128.6, 128.4, 128.4, 128.3, 114.6, 76.3, 73.6, 72.9,
69.4, 61.6, 55.6, 36.4, 22.0, 21.0.
HRMS (ESI): m/z [M + NH4]+ calcd for C28H35N4O7S: 571.2221; found:
571.2218.
(8) Santander, V. M.; Cue, A. B.; Diaz, J. G. H.; Balmis, F. J.; Miranda,
G.; Urbina, E.; Portilla, J.; Plata, A. A.; Zapata, H. B.; Munoz, V. A.;
Abreu, L. M. Rev. Invest. Biol. Univ. Guadalajara 1961, 1, 94.
(9) (a) Frye, W. W.; Mule, J. G.; Swartzwelder, C. Antibiot. Annu.
1955, 820. (b) Armstrong, T.; Santa Maria, O. Antibiot. Annu.
1955, 824.
(10) Korzybski, T.; Kowszyk-Gindifer, Z.; Kurytowicz, W. Antibiotics;
Vol. 1; American Society of Microbiology: Washington DC,
1978, 343–346.
(11) (a) Kim, J. H.; Curtis-Long, M. J.; Woo, D. S.; Jin, H. L.; Byong, W.
L.; Yong, J. Y.; Kyu, Y. K.; Park, K. H. Bioorg. Med. Chem. Lett.
2005, 15, 4282. (b) Chapman, T. M.; Courtney, S.; Hay, P.; Davis,
B. G. Chem.Eur. J. 2003, 9, 3397.
(2S,3R,4R)-4-Hydroxy-2-(4-methoxybenzyl)pyrrolidin-3-yl Ace-
tate Hydrochloride [(+)-Anisomycin 1b)]
To a solution of compound 9 (56 mg, 0.10 mmol) in MeOH (2 mL) was
added HCl (1 drop) and catalytic amount of Pd/C (10% on carbon) and
the mixture stirred under a positive pressure of H2 (balloon) at r.t. for
12 h. After completion of the reaction, Pd/C was filtered off through a
short pad of Celite and the filtrate was concentrated under reduced
pressure to give a residue that was purified by flash column chroma-
tography (MeOH/CHCl3, 5:95) to afford 1b (19 mg, 72%) as a white
solid; Rf = 0.54 (MeOH/CHCl3, 1:9); mp 109–111 °C.
[α]D –3.8 (c 0.24, MeOH) {Lit.13e [α]D –3.6; Lit.12f [α]D +4.0 (c 0.28,
26
25
MeOH) for (–)-anisomycin}.
(12) For recent literature: (a) Zeng, J.; Zhang, Q.; Zhang, H. K.; Chen,
A. RSC Adv. 2013, 3, 20298. (b) Li, J.; Feng, Y. H.; Li, X. B.; Han,
W.; Liu, H. Q.; Shao, G. G. Chin. Chem. Lett. 2012, 23, 647.
(c) Chouthaiwale, P. V.; Kotkar, S. P.; Sudalai, A. ARKIVOC 2009,
(ii), 88. (d) Joo, J.-E.; Lee, K.-Y.; Pham, V.-T.; Tian, Y-S.; Ham, W.-
H. Org. Lett. 2007, 9, 3627. (e) Kim, J. H.; Curtis-Long, M. J.; Seo,
W. D.; Ryu, Y. B.; Yang, M. S.; Park, K. H. J. Org. Chem. 2005, 70,
4082; and references cited therein. (f) Hulme, A. N.; Rosser, E.
M. Org. Lett. 2002, 4, 265; and references cited therein.
(13) (a) Detz, R. J.; Abiri, Z.; Griel, R. L.; Hiemstra, H.; Maarseveen, J.
H. V. Chem. Eur. J. 2011, 17, 5921. (b) Reddy, K. S.; Rao, B. V. Tet-
rahedron: Asymmetry 2011, 22, 190. (c) Reddy, J. S.; Kumar, A.
R.; Rao, B. V. Tetrahedron: Asymmetry 2005, 16, 3154.
(d) Meyers, A. I.; Dupre, B. Heterocycles 1987, 113. (e) Wong, C.
M.; Buccini, J.; Chang, I.; Te Raa, J.; Schwenk, R. Can. J. Chem.
1969, 47, 2421. (f) Wong, C. M.; Buccini, J.; Te Raa, J. Can. J. Chem.
1968, 46, 3091.
IR (neat): 3386, 3284, 3232, 1782, 1621, 1529, 1214, 714 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 7.24–7.26 (m, 2 H), 6.90–6.93 (m, 2 H),
5.06 (d, J = 2.92 Hz, 1 H), 4.16–4.20 (m, 1 H), 3.79 (s, 3 H), 3.63 (dd, J1 =
12.83 Hz, J2 = 4.48 Hz, 1 H), 3.21–3.24 (m, 1 H), 3.03–3.11 (m, 1 H),
2.97–3.00 (m, 1 H), 2.19 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 170.8, 160.5, 130.9, 129.8, 128.9,
115.5, 78.2, 73.4, 63.6, 55.7, 52.6, 32.1, 20.6.
HRMS (ESI): m/z [M + H]+ or [M – Cl]+ calcd for C14H20NO4: 266.1387;
found: 266.1379.
Acknowledgment
S.A. and P.S. thanks the CSIR, New Delhi for awarding Senior Research
Fellowship and also we are thankful to Mr A. K. Pandey for technical
assistance and SAIF, CDRI, for providing spectral data. The financial
grant from DST (SB/S1/OC-28/2014) is gratefully acknowledged. CDRI
Communication No. 9174.
(14) (a) Arora, I.; Kashyap, V. K.; Singh, A. K.; Dasgupta, A.; Kumar, B.;
Shaw, A. K. Org. Biomol. Chem. 2014, 12, 6855. (b) Das, P.;
Kundooru, S.; Pandole, R.; Sharma, S. K.; Singh, B. N.; Shaw, A. K.
Tetrahedron: Asymmetry 2016, 27, 101.
(15) Morillo, M.; Lequart, V.; Grand, E.; Goethals, G.; Usubillaga, A.;
Villa, P.; Martin, P. Carbohydr. Res. 2001, 334, 281.
Supporting Information
(16) Meurillon, M.; Marton, Z.; Hospital, A.; Jordheim, L. P.; Béjaud,
J.; Lionne, C.; Dumontet, C.; Périgaud, C.; Chaloin, L.; Peyrottes,
S. Eur. J. Med. Chem. 2014, 77, 18.
Supporting information for this article is available online at
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ortioInfgrmoaitn
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p
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(17) Mereyala, H. B.; Gadikota, R. R. Tetrahedron: Asymmetry 1998, 9,
827.
(18) Kundooru, S.; Das, P.; Meena, S.; Kumar, V.; Siddiqi, M. I.; Datta,
D.; Shaw, A. K. Org. Biomol. Chem. 2015, 13, 8241.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, 1191–1196