D
A. Sengupta, S. Hosokawa
Letter
Synlett
EtO
EtO
Ot-Bu
P
O
O
DIBAL
14
N
O
13
10
CH2Cl2
−78 °C
LiHMDS, THF
−78 to −25 °C, 16 h
68% in 2 steps
OTBS
O
O
OTBS
O
12
13
H2, Pd/C
Ot-Bu
Ot-Bu
EtOH
rt, 3 h
OTBS
O
OTBS
O
15
16
2
2,4,6-Cl3C6H2COCl
Et3N, THF
HF•Py
13
OH
Ot-Bu
10
then DMAP, toluene
MeCN
rt, 15 min
88% in 2 steps
rt, 4 h
76%
O
3
O
O
OTBS
OH
1) TFA
CH2Cl2
rt, 15 min
O
O
O
N
N
Boc CO2t-Bu
O
2) BOPCl
Et3N
O
CH2Cl2
0 °C, 48 h
50% in 2 steps
17
PF1163B (1)
Scheme 4 Completion of total synthesis of PF1163B (1)
Funding Information
(5) Nakamura, T.; Kubota, K.; Ieki, T.; Hosokawa, S. Org. Lett. 2016,
18, 132.
We are grateful for the financial support from the Sumitomo Founda-
tion and the Tokyo Biochemical Research Foundation. This work was
also supported by Grant-in-Aid for Scientific Research on Innovative
Areas ‘Frontier Research on Chemical Communications’ (Grant no.
18H04632).()
(6) Zurabishvlli, D. S.; Bukia, T. J.; Lomidze, M. O.; Trapaidze, M. V.;
Elizbarashvili, E. N.; Samsoniya, S. A.; Doroshenko, T. V.;
Kazmaier, U. Chem. Heterocyclic Comp. 2015, 51, 139.
(7) Sengupta, A.; Hosokawa, S. Tetrahedron Lett. 2019, 60, 411.
(8) Ma, J.; Cheon, H. S.; Kishi, Y. Org. Lett. 2007, 9, 319.
(9) For synthesis of 2: See Supporting Information.
(10) Synthesis of PF1163B (1) from Acyclic 17
Supporting Information
To a solution of compound 17 (85.9 mg, 0.114 mmol) in CH2Cl2
(4.0 mL) at 0 °C was added TFA (1.0 mL, 98%). The reaction
mixture was stirred for 35 min at rt and then concentrated. The
residue was then taken up in CH2Cl2 (64.0 mL) and cooled to
0 °C. Et3N (0.19 mL, 1.368 mmol) was added dropwise, followed
by the addition of BOP-Cl (174.1 mg, 0.684 mmol). The reaction
mixture was stirred at 0 °C for 48 h. Then, it was concentrated
and NaHCO3 aq. (2.0 mL) was added. The aqueous layer was
extracted two times with CHCl3 (4.0 mL × 2) and the combined
organic layers were concentrated, dried with Na2SO4, and puri-
fied by silica gel chromatography (n-hexane/EtOAc = 5:1) to
give PF1163B (1) (27.0 mg, 0.058 mmoles, 50% over 2 steps) as a
colorless oil. Rf = 0.48 (n-hexane/EtOAc = 1:1). [α]D23 = –109.6 (c
0.49, MeOH). 1H NMR (400 MHz, CDCl3): δ = 7.21–7.05 (2 H, m),
6.88–6.79 (2 H, m), 5.84–5.75 (0.6 H, m), 4.94–4.78 (1 H, m),
4.60–4.54 (0.27 H, m), 4.09–4.01 (2 H, m), 3.99–3.91 (2 H, m),
3.60–3.14 (4 H, m), 3.04–2.90 (3 H, m), 2.84–2.61 (2 H, m),
Supporting information for this article is available online at
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References and Notes
(1) (a) Nose, H.; Seki, A.; Yaguchi, T.; Hosoya, A.; Sasaki, T.; Hoshiko,
S.; Shomura, T. J. Antibiot. 2000, 53, 33. (b) Sasaki, T.; Nose, H.;
Hosoya, A.; Yoshida, S.; Kawaguchi, M.; Watanabe, T.; Usui, T.;
Ohtsuka, Y.; Shomura, T. J. Antibiot. 2000, 53, 38.
(2) Tatsuta, K.; Takano, S.; Ikeda, Y.; Nakano, S.; Miyazaki, S. J. Anti-
biot. 1999, 52, 1146.
(3) Bouazza, F.; Brigitte, R.; Bachmann, C.; Gesson, J. P. Org. Lett.
2003, 5, 4049.
(4) (a) Shirokawa, S.; Kamiyama, M.; Nakamura, T.; Okada, M.;
Nakazaki, A.; Hosokawa, S.; Kobayashi, S. J. Am. Chem. Soc. 2004,
126, 13604. (b) Mukaeda, Y.; Kato, T.; Hosokawa, S. Org. Lett.
2012, 14, 5298. (c) Tsukada, H.; Mukaeda, Y.; Hosokawa, S. Org.
Lett. 2013, 15, 678. (d) Sagawa, N.; Sato, H.; Hosokawa, S. Org.
Lett. 2017, 19, 198. (e) Sagawa, N.; Moriya, H.; Hosokawa, S. Org.
Lett. 2017, 19, 250. (f) Hosokawa, S. J. Syn. Org. Chem., Jpn 2017,
75, 831. (g) Hosokawa, S. Acc. Chem. Res. 2018, 51, 1301.
2.47–1.96 (4 H, m), 1.54–1.03 (16 H, m), 0.92–0.79 (6 H, m). 13
C
NMR (100 MHz, CDCl3): δ = 173.4, 171.1, 170.2, 157.2, 130.2,
129.7, 129.1, 114.9, 114.4, 75.3, 69.1, 69.0, 61.5, 55.4, 35.1, 35.0,
34.0, 33.7, 33.6, 33.5, 31.7, 31.6, 29.4, 29.3, 28.7, 26.5, 25.0, 20.5,
14.0. HRMS-ESI: m/z [M
484.3033; found: 484.3033. IR (KBr): 3400, 2950, 2929, 1731,
1632, 1512, 1248, 1220, 1078, 772 cm–1
+
Na]+ calcd for C27H43O5NNa:
.
© Georg Thieme Verlag Stuttgart · New York — Synlett 2019, 30, A–D