1
492
K. H. Kim et al. / Tetrahedron Letters 53 (2012) 1490–1492
at the Korea Basic Science Institute for their aid in the NMR and MS
spectra measurements.
11. Isaka, M.; Palasarn, S.; Lapanun, S.; Sriklung, K. J. Nat. Prod. 2007, 70, 675.
2. First, to break the connectivity of C-1 and –NH–C-8, following reaction was
performed. To a solution of turtschamide (1, 2.0 mg) in CH CN (9.0 mL) and
glacial acetic acid (3.0 mL) was added NaCNBH (3.0 mmol) and the reaction
mixture was heated at 55 °C for 12 h, cooled to room temperature, evaporated
to dryness and redissolved in CH Cl . The organic layer was washed with 1 N
NaOH, brine and filtered through Na SO , concentrated. Then, the reaction
mixture was hydrolyzed by heating in 6 N HCl (1 mL) at 110 °C for 15 h. After
cooling, the solution was evaporated to dryness and dissolved in H O (150 L).
To this solution was added 1% (w/v) FDAA (Marfey’s reagent, N -(2,4-dinitro-5-
fluorophenyl)- -alaninamide) in acetone (300 L) and 1 M NaHCO solution
(70 L) and the mixture was incubated at 40 °C for 1 h. The reaction was
quenched by the addition of 1 M HCl (70 L) and the resulting homogeneous
solution was diluted with MeOH (1.0 mL). Standard - and -Tyr were also
1
3
3
Supplementary data
2
2
2
4
2
l
a
L
l
3
References and notes
l
l
1.
2.
3.
4.
5.
6.
7.
Nawrot, R.; Wolun-Cholewa, M.; Bialas, W.; Wyrzykowska, D.; Balcerkiewicz,
S.; Gozdzicka-Jozefiak, A. BMC Complement. Altern. Med. 2010, 10, 78.
Lee, K. H.; Huh, J. W.; Choi, M. M.; Yoon, S. Y.; Yang, S. J.; Hong, H. N.; Cho, S. W.
Exp. Mol. Med. 2005, 37, 371.
Hung, T. M.; Na, M. K.; Dat, N. T.; Ngoc, T. M.; Youn, U. J.; Kim, H. J.; Min, B. S.;
Lee, J. P.; Bae, K. H. J. Ethnopharmacol. 2008, 119, 74.
L
D
derivatized with FDAA in the same manner as that of the hydrolyzate of 1. Five
microliters of the FDAA derivatives were analyzed by HPLC using an ODS
column. HPLC analysis was performed with the following conditions: INNO
Column (INNOPIA Co., 10.0 ꢀ 250 mm, 5
phase MeCN/(0.05% TFA in H O), 25:75, flow rate 1.0 mL/min, UV detection at
340 nm. Retention times (min) of the FDAA amino acid derivatives used as
standards were as follows: -Tyr (19.9 min), and -Tyr (27.4 min). The HPLC
lm, iP-ODS-N-120-5 lm), mobile
2
Matsuda, H.; Shiomoto, H.; Naruto, S.; Namba, K.; Kubo, M. Planta Med. 1988,
54, 27.
L
D
Kim, K. H.; Lee, I. K.; Piao, C. J.; Choi, S. U.; Lee, J. H.; Kim, Y. S.; Lee, K. R. Bioorg.
Med. Chem. Lett. 2010, 20, 4487.
Kim, K. H.; Lee, I. K.; Choi, S. U.; Lee, J. H.; Moon, E.; Kim, S. Y.; Lee, K. R. Planta
Med. 2011, 77, 1555.
chromatogram of the derivatized hydrolyzate of 1 contained a peak of L-Tyr
(19.9 min).
13. Chaidir; Lin, W. H.; Ebel, R.; Edrada, R. A.; Wray, V.; Nimtz, M.; Sumaryono, W.;
Proksch, P. J. Nat. Prod. 2001, 64, 1216.
14. Duong, T. N.; Edrada, R.; Ebel, R.; Wray, V.; Frank, W.; Duong, A. T.; Lin, W. H.;
Proksch, P. J. Nat. Prod. 2007, 70, 1640.
15. Abdelfattah, M. S.; Toume, K.; Ahmed, F.; Sadhu, S. K.; Ishibashi, M. Chem.
Pharm. Bull. 2010, 58, 1116.
16. Saifah, E.; Suttisri, R.; Shamsub, S.; Pengsuparp, T.; Lipipun, V. Phytochemistry
1999, 52, 1085.
Kim, K. H.; Piao, C. J.; Choi, S. U.; Son, M. W.; Lee, K. R. Planta Med. 2010, 76,
1
732.
8
9
.
.
Lee, H. Y.; Kim, C. W. Kor. J. Pharmacogn. 1999, 30, 332.
2
5
Turtschamide (1): amorphous gum; ½
MeOH) nm (log ): 204 (4.18), 245 (4.12), 286 (2.78), 313 (1.71); IR (KBr):
3
max = 3336, 2944, 1690, 1456, 1278, 1056, 675 cm OD, 500 MHz)
+
aꢁ : ꢂ15.7 (c 0.25, MeOH); UV kmax
D
(
m
e
ꢂ1
1
;
H (CD
13
and C NMR (CD
HR-ESI-MS m/z 370.1770 [M+H] (calcd for C20
0. Marfey, P. Carsberg Res. Commun. 1984, 49, 591.
3
OD, 125 MHz): see Table 1; ESI-MS m/z 370 [M+H] ; positive
17. Skehan, P.; Storeng, R.; Scudiero, D.; Monks, A.; McMahon, J.; Vistica, D.;
Warren, J. T.; Bokesch, H.; Kenney, S.; Boyd, M. R. J. Natl. Cancer Inst. 1990, 82,
1107.
+
24 3 4
H N O , 370.1767).
1