F. Zhang, Y. Jia / Tetrahedron 65 (2009) 6840–6843
6843
Then diluted with CH2Cl2 (20 mL) and added 0.2 N aqueous
NaOH with vigorous stirring to adjust the PH of aqueous layer
to 11–12. The aqueous layer was extracted with CH2Cl2
(5ꢂ10 mL). The combined organic layers were dried over an-
hydrous Na2SO4, filtered and concentrated in vacuo. The residue
was purified by column chromatography on silica gel (CH2Cl2/
MeOH/NH4OH, 150:10:1) to afford 13 accompanied with DMAP.
The mixture was further purified by a column chromatogram of
46.09, 45.9, 45.8, 41.8, 41.2, 40.41, 40.37, 37.4, 37.3, 30.30, 30.26,
29.7, 29.2, 17.1, 16.9, 14.9, 14.4; HRMS (ESI) m/z calcd for C42H59N2O8
[MþH]þ 719.4271; found 719.4288.
Acknowledgements
Financial support from Peking University and National Science
Foundation of China (NO. 20842004, 20802005) and the Ph.D.
Programs Foundation of Ministry of Education of China (No.
200800011055) are greatly appreciated.
Sephadex LH-20 (CH2Cl2/MeOH, 1:1) to give pure 13 (65 mg,
23
80%) as a pale yellow amorphous solid. [
a
]
ꢀ21.6 (c 1.49,
D
CHCl3); 1H NMR (400 MHz, CDCl3)
d
7.76 (m, 4H), 7.32 (m, 4H),
7.08 (m, 2H), 6.85–6.76 (m, 4H), 4.87–4.81 (m, 2H), 4.40–4.31
(m, 2H), 3.88–3.79 (m, 2H), 3.62 (s, 3H), 3.60 (s, 3H), 2.58 (m,
2H), 2.48–2.44 (m, 2H), 2.46 (s, 6H), 2.23–2.13 (m, 1H), 2.20 (s,
6H), 2.10–1.92 (m, 3H), 1.90–1.80 (m, 3H), 1.78–1.74 (m, 1H),
1.72–1.56 (m, 4H), 1.48–1.41 (m, 2H), 1.20–1.14 (m, 1H), 0.78 (d,
J¼6.8 Hz, 3H), 0.77 (d, J¼7.2 Hz, 3H), 0.74 (d, J¼6.8 Hz, 3H),
0.72–0.66 (m, 1H), 0.57 (d, J¼7.6 Hz, 3H); 13C NMR (100 MHz,
Supplementary data
Experimental details and NMR spectra. This material is avail-
able. Supplementary data associated with this article can be found
References and notes
CDCl3)
d 171.2, 151.7, 145.00, 144.98, 139.1, 138.9, 137.6, 137.5,
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133.5, 129.41, 129.40, 128.5, 128.4, 123.9, 119.6, 119.2, 112.50,
112.46, 77.15, 77.02, 57.7, 57.5, 57.4, 57.2, 55.7, 47.4, 46.8, 46.2,
46.1, 46.0, 45.9, 41.7, 41.3, 40.5, 40.3, 37.5, 37.4, 30.5, 30.4, 30.0,
29.2, 21.7, 17.2, 17.0, 14.7, 14.4; MS (ESI–TOF, possitive), 1027.5
[MþH]þ.
4.5. (L)-Incarvillateine 1
Deprotection of the tosyl groups in 13 (92 mg, 0.09 mmol)
employed sodium/anthracene conditions previous reported.3b Af-
ter 13 reacted completely monitoring by TLC, the reaction mixture
was quenched with saturated aqueous NaHCO3 (10 mL). The
aqueous layer was extracted with CH2Cl2 (5ꢂ20 mL). The combined
organic layers were dried over anhydrous Na2SO4, filtered and
concentrated in vacuo. The crude materials was purified by column
chromatography on silica gel (CH2Cl2/MeOH/NH4OH, 150:10:1) to
23
afford 1 (54 mg, 85%) as a white solid. [
NMR (400 MHz, CDCl3)
a]
ꢀ14.8 (c 1.39, CHCl3); 1H
D
d
6.83–6.78 (m, 6H), 4.93–4.85 (m, 2H),
4.39–4.29 (m, 2H), 3.90–3.81 (m, 2H), 3.89 (s, 3H), 3.87 (s, 3H),
2.60–2.55 (m, 2H), 2.50–2.45 (m, 2H), 2.19 (s, 6H), 2.17–2.08 (m,
1H), 2.03–1.90 (m, 3H), 1.87–1.80 (m, 3H), 1.77–1.67 (m, 2H), 1.63–
1.54 (m, 3H), 1.44 (t, J¼12.0 Hz, 2H), 1.06 (m, 1H), 0.81 (d, J¼7.6 Hz,
3H), 0.76 (d, J¼6.8 Hz, 3H), 0.72 (d, J¼6.8 Hz, 3H), 0.60 (d, J¼7.2 Hz,
3H), 0.58–0.54 (m, 1H); 13C NMR (100 MHz, CDCl3)
d 171.9, 171.7,
6. Sakakura, A.; Kawajiri, K.; Ohkubo, T.; Kosugi, Y.; Ishihara, K. J. Am. Chem. Soc.
2007, 129, 14775–14779.
7. He, X.; Lin, W. H.; Xu, R. S. Acta Chim. Sinica 1990, 48, 694–699.
146.73, 146.65, 145.3, 145.1, 130.7, 130.5, 120.4, 119.9, 114.6, 110.85,
110.76, 76.6, 76.4, 57.6, 57.5, 57.3, 57.2, 55.83, 55.78, 47.9, 47.3, 46.13,