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S.-i. Inoue et al.
PAPER
H, CH3(CH2)2CHH¢], 1.55–1.64 [m, 1 H, CH3(CH2)2CHH¢], 1.88–
2.12 [m, 5 H, (CH3)2CH and (CH2)2CH2N], 2.15 (dd, J = 14.5, 7.0
Hz, 1 H, CHH¢CONHOH), 2.31 (dd, J = 14.5, 7.0 Hz, 1 H,
CHH¢CONHOH), 2.75–2.84 (m, 1 H, CHCH2CONHOH), 3.50 (dd,
J = 11.0, 6.0 Hz, 1 H, CHH¢OH), 3.53–3.62 (m, 1 H, CHH¢N), 3.64
(dd, J = 11.0, 5.0 Hz, 1 H, CHH¢OH), 3.82–3.90 (m, 1 H, CHH¢N),
4.08–4.18 (m, 1 H, CH2CHN), 4.38 (d, J = 8.5 Hz, 1 H, CHCO),
8.11 (d, J = 8.0 Hz, 1 H, NH or OH).
f = 4.0 cm, l = 10 cm; EtOAc) to give 20 as a colorless amorphous
powder; yield: 1.04 g (62%); [a]D24 –20.3 (c = 1.2, MeOH).
IR (neat): 1620, 1650, 1670, 3240, 3400 cm–1.
1H NMR (500 MHz, CDCl3): d = 0.91 (t, J = 7.0 Hz, 3 H, CH3CH2),
0.94 [t, J = 7.0 Hz, 3 H, (CH3)2CH], 0.99 [t, J = 7.0 Hz, 3 H,
(CH3)2CH], 1.30–1.45 [m, 4 H, CH3(CH2)2], 1.56–1.65 [m, 1 H,
(CH3)2CH], 1.84–2.12 [m, 4 H, (CH2)2CH2N], 2.22–2.32 [m, 2 H,
CH3(CH2)2CH2], 3.10 (s, 2 H, CH2CONHOBn), 3.50 (dt, J = 10.0,
7.5 Hz, 1 H, CHH¢N), 3.58 (dd, J = 11.0, 7.5 Hz, 1 H, CHH¢OH),
3.69 (dd, J = 11.0, 3.0 Hz, 1 H, CHH¢OH), 3.80–3.87 (m, 1 H,
CHH¢N), 4.26 (dddd, J = 7.5, 7.5, 7.5, 3.0 Hz, 1 H, CH2CHN), 4.59
(dd, J = 8.0, 8.0 Hz, 1 H, CHCO), 4.88 (s, 2 H, NHOCH2Ph), 6.30
(t, J = 6.5 Hz, 1 H, CH=C), 6.71 (d, J = 8.0 Hz, 1 H, NH), 7.25–7.40
(m, 5 H, ArH), 9.81 (br s, 1 H, NHOBn).
FAB-HRMS: m/z calcd for C19H36N3O5: 386.2655; found:
386.2632.
17
This compound was identified to be the same as that obtained by
catalytic hydrogenation (H2, Pd/C) of 1; colorless amorphous pow-
der; [a]D22 –49.0 (c = 2.2, MeOH).
13C NMR (75 MHz, CDCl3): d = 13.79, 17.84, 19.28, 22.34, 24.31,
27.72, 28.37, 30.63, 31.45, 33.36, 48.15, 56.07, 61.05, 66.43, 77.88,
128.28, 128.76, 128.97, 135.40, 140.06, 168.04, 19.78, 172.53.
IR (CHCl3): 1622, 1680, 3340 cm–1.
1H NMR (500 MHz, CD3OD): d = 0.88 (t, J = 7.0 Hz, 3 H,
CH3CH2), 0.96 [d, J = 7.0 Hz, 3 H, (CH3)2CH], 0.99 [d, J = 7.0 Hz,
3 H, (CH3)2CH], 1.19–1.38 [m, 6 H, CH3(CH2)2], 1.38–1.46 [m, 1
H, CH3(CH2)2CHH¢], 1.50–1.64 [m, 1 H, CH3(CH2)2CHH¢], 1.86–
2.13 [m, 5 H, (CH3)2CH and (CH2)2CH2N], 2.30 (dd, J = 15.0, 6.0
Hz, 1 H, CHH¢CONH2), 2.48 (dd, J = 15.0, 8.5 Hz, 1 H,
CHH¢CONH2), 2.73–2.82 (m, 1 H, CHCH2CONH2), 3.50 (dd,
J = 10.5, 6.0 Hz, 1 H, CHH¢OH), 3.54–3.62 (m, 1 H, CHH¢N), 3.66
(dd, J = 10.5, 4.5 Hz, 1 H, CHH¢OH), 3.88 (ddd, J = 10.0, 7.0, 7.0
Hz, 1 H, CHH¢N), 4.07–4.16 (m, 1 H, CH2CHN), 4.39 (d, J = 8.5
Hz, 1 H, CHCO), 8.03 (d, J = 8.0 Hz, 1 H, NH or OH).
FAB-MS: m/z = 474 (M+ + 1).
FAB-HRMS: m/z calcd for C26H40N3O5: 474.2968; found:
474.2951.
Actinonin (1) and Epiactinonin (epi-1)
To 20 (91.4 mg, 193 mmol) and pyridine (50 mL) in EtOH (2.5 mL)
was added 10% Pd/C (52.6 mg) at r.t. and the mixture was stirred at
the same temperature for 70 min under H2 atmosphere. After filtra-
tion and removal of the solvent, the residue was subjected to column
chromatography (Wako gel C = 200, f = 1.8 cm, l = 9.5 cm; i-
PrOH–EtOAc, 1:7–1:3) to give 1 (32.1 mg, 43%) and epi-1 (28.2
mg, 38%).
FAB-MS: m/z = 370 (M+ + 1).
FAB-HRMS: m/z calcd for C19H36N3O4: 370.2706; found:
370.2712.
Acknowledgment
epi-17
This compound was identified with the same as that one obtained by
catalytic hydrogenation (H2, Pd/C) of epi-1; colorless amorphous
powder; [a]D22 –66.6 (c = 2.0, MeOH).
We are grateful to the SC-NMR Laboratory of Okayama University
for the use of the facilities.
IR (CHCl3): 1628, 1670, 3335 cm–1.
References
1H NMR (500 MHz, CD3OD): d = 0.90 (t, J = 7.0 Hz, 3 H,
CH3CH2), 0.97 [d, J = 7.0 Hz, 3 H, (CH3)2CH], 1.00 [d, J = 7.0 Hz,
3 H, (CH3)2CH], 1.22–1.36 [m, 6 H, CH3(CH2)2], 1.42–1.51 [m, 1
H, CH3(CH2)3CHH¢], 1.53–1.66 [m, 1 H, CH3(CH2)2CHH¢], 1.86–
2.12 [m, 5 H, (CH3)2CH and (CH2)2CH2N], 2.30 (dd, J = 15.0, 7.0
Hz, 1 H, CHH¢CONH2), 2.48 (dd, J = 15.0, 7.5 Hz, 1 H,
CHH¢CONH2), 2.72–2.80 (m, 1 H, CHCH2CONH2), 3.44–3.61 (m,
2 H, CHH¢OH and CHH¢N), 3.66 (dd, J = 10.5, 4.5 Hz, 1 H,
CHH¢OH), 3.82–3.92 (m, 1 H, CHH¢N), 4.07–4.18 (m, 1 H,
CH2CHN), 4.40 (d, J = 8.5 Hz, 1 H, CHCO).
(1) (a) Gordon, J. J.; Kelly, B. K.; Miller, G. A. Nature 1962,
195, 701. (b) Gordon, J. J.; Devlin, J. P.; East, A. J.; Ollis,
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FAB-HRMS: m/z calcd for C19H36N3O4: 370.2706; found:
370.2704.
(1¢S,2¢¢S)-N-Benzyloxy-N¢-{1-[(2-hydroxymethyl)pyrrolidinyl-
carbonyl]-2-methylpropyl}-3-[(E)-pentylidene]succinamide)
(20)
To a solution of 192a (708 mg, 3.54 mmol) in anhyd CHCl3 (25 mL)
was added 15 (1.25 g, 4.58 mmol) at r.t. and the mixture was stirred
at the same temperature for 4 d under an argon atmosphere. The
mixture was poured into EtOAc (180 mL) and the organic layer was
washed with sat. aq NaHCO3 (60 mL), H2O (60 mL), and brine (40
mL), and dried (MgSO4). After removal of the solvent, the residue
was subjected to column chromatography (Wako gel C = 200,
(6) Akiyama, M.; Shimizu, K.; Aiba, S.; Banba, F. J. Chem.
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Synthesis 2011, No. 11, 1705–1710 © Thieme Stuttgart · New York