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H. Park et al.
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Synthesis
0.5 H), 5.00 (d, J = 12.6 Hz, 0.5 H), 4.92 (d, J = 12.0 Hz, 0.5 H), 4.24 (br s,
1 H), 3.62 (br s, 0.5 H), 3.47 (br s, 0.5 H), 3.39 (br s, 1 H), 2.00–1.62 (m,
5 H), 1.40–1.19 (m, 7 H), 0.83 (br s, 3 H).
1 H), 3.62–3.53 (m, 1 H), 3.47–3.39 (m, 1 H), 3.31 (t, J = 8.9 Hz, 0.5 H),
3.25 (t, J = 9.0 Hz, 0.5 H), 2.71–2.66 (m, 1 H), 2.10–2.05 (m, 1 H), 1.81–
1.74 (m, 1 H).
13C NMR (CDCl3, 125 MHz): δ (two rotamers, 1:1) = 166.2 (0.5 C),
166.0 (0.5 C), 155.5 (0.5 C), 155.2 (0.5 C), 136.8 (0.5 C), 136.7 (0.5 C),
132.8, 130.3 (0.5 C), 130.2 (0.5 C), 129.8, 129.6, 128.3 (3 C), 127.95,
127.89, 127.7 (2 C), 75.7 (0.5 C), 75.3 (0.5 C), 67.0 (0.5 C), 66.6 (0.5 C),
59.6 (0.5 C), 58.8 (0.5 C), 47.1 (0.5 C), 46.5 (0.5 C), 31.6, 31.5 (0.5 C),
30.5 (0.5 C), 28.0 (0.5 C), 27.7 (0.5 C), 25.3, 23.9 (0.5 C), 23.3 (0.5 C),
22.4, 13.9.
13C NMR (CDCl3, 125 MHz): δ = 166.3, 154.7, 136.8, 133.0, 129.8,
129.5 (2 C), 128.4 (2 C), 128.3 (2 C), 127.9 (2 C), 127.8, 66.7, 65.7, 49.0
(0.5 C), 48.5 (0.5 C), 45.5 (0.5 C), 45.1 (0.5 C), 38.2 (0.5 C), 37.2 (0.5 C),
28.4 (0.5 C), 27.6 (0.5 C).
HRMS (FAB): m/z [M + H]+ calcd for C20H22NO4: 340.1549; found:
340.1543.
HRMS (FAB): m/z [M + H]+ calcd for C25H32NO4: 410.2331; found:
410.2342.
Acknowledgment
This work was supported by the Mid-Career Researcher Program
(NRF-20165R 2A1A05005375) of the National Research Foundation of
Korea (NRF) grant funded by the Korean government (MSIP).
tert-Butyl (R*)-2-[(R*)-1-(Benzoyloxy)hexyl]pyrrolidine-1-carbox-
ylate (5d)
Yield: 167 mg (89%); colorless oil.
IR (neat): 2961, 2874, 1719, 1696, 1389, 1271, 1170, 1110, 711 cm–1
.
1H NMR (CDCl3, 500 MHz): δ (two rotamers, 1:1) = 8.04–7.98 (m, 2 H),
7.53–7.47 (m, 1 H), 7.42–7.37 (m, 2 H), 5.42 (br s, 0.5 H), 5.10 (br s, 0.5
H), 4.13 (br s, 0.5 H), 4.06 (br s, 0.5 H), 3.55 (br s, 0.5 H), 3.31 (br s, 1.5
H), 1.93–1.60 (m, 6 H), 1.50–1.32 (m, 2 H), 1.45 (s, 4 H), 1.23 (s, 9 H),
0.85–0.82 (m, 3 H).
Supporting Information
Supporting information for this article is available online at
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13C NMR (CDCl3, 125 MHz): δ (two rotamers, 1:1) = 166.3 (0.5 C),
165.9 (0.5 C), 154.9 (0.5 C), 154.8 (0.5 C), 132.8 (0.5 C), 132.6 (0.5 C),
130.4, 129.8, 129.6, 128.3, 128.1, 79.7 (0.5 C), 78.9 (0.5 C), 75.4 (0.5 C),
75.1 (0.5 C), 58.9 (0.5 C), 58.6 (0.5 C), 46.8 (0.5 C), 46.5 (0.5 C), 31.6
(1.5 C), 29.6 (0.5 C), 28.4, 28.3, 28.2, 27.7 (0.5 C), 27.5 (0.5 C), 25.5 (0.5
C), 25.1 (0.5 C), 23.9 (0.5 C), 23.4 (0.5 C), 22.4, 13.9.
References
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(b) Modern Alkaloids: Structure, Isolation, Synthesis and Biology;
Fattorusso, E.; Taglialatela-Scafati, O., Eds.; Wiley-VCH: Wein-
heim, 2008.
HRMS (FAB): m/z [M + H]+ calcd for C22H34NO4: 376.2488; found:
(2) (a) Greene, T. W.; Wuts, P. G. M. Greene’s Protective Groups in
Organic Synthesis; Wiley: New York, 2007. (b) Kociensiki, P. J.
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376.2491.
(9H-Fluoren-9-yl)methyl (R*)-2-[(R*)-1-(Benzoyloxy)hexyl]pyrro-
lidine-1-carboxylate (5e)
Yield: 182 mg (91%); colorless oil.
IR (neat): 2958, 2874, 2253, 1711, 1415, 1272, 1111, 905, 725 cm–1
.
(4) For recent selected examples, see: (a) Ahuja, B. B.; Sudalai, A.
Tetrahedron: Asymmetry 2015, 26, 24. (b) Dharuman, S.;
Palanivel, A. K.; Vankar, Y. D. Org. Biomol. Chem. 2014, 12, 4983.
(c) Kikuchi, H.; Horoiwa, S.; Kasahara, R.; Hariguchi, N.;
Matsumoto, M.; Oshima, Y. Eur. J. Med. Chem. 2014, 76, 10. (d) Li,
Q. R.; Dong, G. R.; Park, S. J.; Hong, Y. R.; Kim, I. S.; Jung, Y. H. Eur.
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Cordero-Vargas, A. Synlett 2013, 24, 2073. (f) Kato, A.; Okaki, T.;
Ifuku, S.; Sato, K.; Hirokami, Y.; Iwaki, R.; Kamori, A.; Nakagawa,
S.; Adachi, I.; Kiria, P. G.; Onomura, O.; Minato, D.; Sugimoto, K.;
Matsuya, Y.; Toyooka, N. Bioorg. Med. Chem. 2013, 21, 6565.
(5) For selected examples, see: (a) Nair, L. G.; Saksena, A.; Lovey, R.;
Sannigrahi, M.; Wong, J.; Kong, J.; Fu, X.; Girijavallabhan, V.
J. Org. Chem. 2010, 75, 1285. (b) Achmatowicz, M.; Hegedus, L. S.
J. Org. Chem. 2004, 69, 2229. (c) Tercel, M.; Denny, W. A. J. Chem.
Soc., Perkin Trans. 1 1998, 509. (d) Van Betsbrugge, J.; Tourwé,
D.; Kaptein, B.; Kierkels, H.; Broxterman, R. Tetrahedron 1997,
53, 9233. (e) Muratake, H.; Matsumura, N.; Natsume, M. Chem.
Pharm. Bull. 1995, 43, 1064. (f) Moody, C. M.; Starkmann, B. A.;
Young, D. W. Tetrahedron Lett. 1994, 35, 5485.
1H NMR (CDCl3, 500 MHz): δ (two rotamers, 1:1) = 8.07 (d, J = 7.1 Hz,
1.2 H), 7.96 (br s, 0.8 H), 7.76–7.62 (m, 2.4 H), 7.49 (br s, 1.6 H), 7.42–
7.25 (m, 7 H), 5.23 (br s, 1 H), 4.53 (br s, 0.4 H), 4.33–4.15 (m, 2 H),
4.10 (t, J = 9.6 Hz, 1 H), 3.93 (br s, 0.6 H), 3.58 (br s, 0.4 H), 3.52–3.43
(m, 1.2 H), 3.39 (br s, 0.4 H), 2.08–1.61 (m, 5 H), 1.45–1.24 (m, 7 H),
0.87 (br s, 3 H).
13C NMR (CDCl3, 125 MHz): δ (two rotamers, 0.6:0.4) = 165.2 (0.6 C),
165.9 (0.4 C), 155.3, 144.3 (0.6 C), 144.2 (0.4 C), 143.9 (0.4 C), 143.7
(0.6 C), 141.2 (1.2 C), 141.0 (0.8 C), 132.7, 130.1, 129.7 (1.2 C), 129.5
(0.8 C), 128.1 (2 C), 127.4, (2 C), 126.8 (2 C), 125.1, 125.0 (0.4 C), 124.8
(0.6 C), 119.7 (2 C) 75.5 (0.6 C), 74.8 (0.4 C), 67.1 (0.4 C), 66.9 (0.6 C),
59.6 (0.6 C), 59.2 (0.4 C), 47.3 (0.4 C), 47.1 (0.6 C), 46.8 (0.4 C), 46.4
(0.6 C), 31.6, 31.5 (0.6 C), 30.8 (0.4 C), 28.1 (0.4 C), 27.7 (0.6 C), 25.2,
23.9 (0.6 C), 23.0 (0.4 C), 22.4, 13.9.
HRMS (FAB): m/z [M + H]+ calcd for C32H36NO: 498.2644; found:
498.2650.
Benzyl 3-[(Benzoyloxy)methyl]pyrrolidine-1-carboxylate (5f)
(6) (a) Ivanov, I.; Nikolova, S.; Aladjov, D.; Stefanova, I.; Zagorchev,
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A. Can. J. Chem. 1994, 72, 23.
(7) Hwang, S.; Park, H.; Kwon, Y.; Kim, S. RSC Adv. 2014, 4, 60017.
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Yield: 158 mg (93%); colorless oil.
IR (neat): 2951, 2880, 1696, 1416, 1267, 1096, 1069, 1025, 709 cm–1
1H NMR (CDCl3, 500 MHz): δ = 8.01 (d, J = 8.0 Hz, 2 H), 7.54 (t, J = 7.3
Hz, 1 H), 7.42 (t, J = 7.2 Hz, 2 H), 7.37–7.31 (m, 4 H), 7.31–7.27 (m, 1
H), 5.13 (s, 2 H), 4.38–4.30 (m, 1 H), 4.25–4.21 (m, 1 H), 3.71–3.62 (m,
.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2017, 49, A–G