D
R. Omura et al.
Paper
Synthesis
13C NMR (125 MHz, CDCl3): δ = 58.0, 60.8, 124.1, 126.6, 128.4, 129.0,
134.4, 135.1, 142.7, 148.3, 192.0.
References
(1) (a) Adger, B. M.; Barkley, J. V.; Bergeron, S.; Cappi, M. W.;
Flowerdew, B. E.; Jackson, M. P.; McCague, R.; Nugent, T. C.;
Roberts, S. M. J. Chem. Soc., Perkin Trans. 1 1997, 3501. (b) Lane,
B. S.; Burgess, K. Chem. Rev. 2003, 103, 2457. (c) Lattanzi, A.;
Russo, A. Tetrahedron 2006, 62, 12264. (d) Mechanisms in Homo-
geneous and Heterogeneous Epoxidation Catalysis; Oyama, S. T.,
Ed.; Elsevier: Amsterdam, 2008, Chap. 1, 3.
Phenyl(3-phenyloxiran-2-yl)methanone (3ga)10c
White solid; yield: 33.6 mg (0.15 mmol, 50%).
1H NMR (400 MHz, CDCl3): δ = 4.09 (d, J = 1.9 Hz, 1 H), 4.31 (d, J = 1.9
Hz, 1 H), 7.37–7.44 (m, 5 H), 7.51 (t, J = 7.7 Hz, 2 H), 7.64 (tt, J1 = 7.5
Hz, J2 = 1.4 Hz, 1 H), 8.03 (dd, J1 = 8.5 Hz, J2 = 1.2 Hz, 2 H).
13C NMR (100 MHz, CDCl3): δ = 59.4, 61.0, 125.8, 128.4, 128.8, 128.9,
(2) For selected reviews on asymmetric epoxidation, see: (a) Adam,
W.; Saha-Möller, C. R.; Ganeshpure, P. A. Chem. Rev. 2001, 101,
3499. (b) Xia, Q.-H.; Ge, H.-Q.; Ye, C.-P.; Liu, Z.-M.; Su, K.-X.
Chem. Rev. 2005, 105, 1603. (c) De Faveri, G.; Ilyashenko, G.;
Watkinson, M. Chem. Soc. Rev. 2011, 40, 1722. (d) Cheong, P. H.
Y.; Legault, C. Y.; Um, J. M.; Çelebi-Ölçüm, N.; Houk, K. N. Chem.
Rev. 2011, 111, 5042. (e) Russo, A.; De Fusco, C.; Lattanzi, A.
ChemCatChem 2012, 4, 901. For selected reports on epoxidation
of α,β-unsaturated carbonyl compounds using hydrogen perox-
ide as an oxidant, see: (f) Bunton, C. A.; Minkoff, G. J. J. Chem.
Soc. 1949, 665. (g) Juliá, S.; Guixer, J.; Masana, J.; Rocas, J.;
Colonna, S.; Molinari, H. J. Chem. Soc., Perkin Trans. 1 1982,
1317. (h) Banfi, S.; Colonna, S.; Molinari, H.; Juliá, S.; Guixer, J.
Tetrahedron 1984, 40, 5207. (i) Ishii, Y.; Sakata, Y. J. Org. Chem.
1990, 55, 5545. (j) Schulz, M.; Kluge, R.; Lipke, M. Synlett 1993,
915. (k) Cativiela, C.; Figueras, F.; Fraile, J. M.; García, J. I.;
Mayoral, J. A. Tetrahedron Lett. 1995, 36, 4125. (l) Kim, Y. H.;
Hwang, J. P.; Yang, S. G. Tetrahedron Lett. 1997, 38, 3009.
(m) Choudary, B. M.; Kantam, M. L.; Bharathi, B.; Reddy, C. V.
Synlett 1998, 1203. (n) Yamaguchi, K.; Mori, K.; Mizugaki, T.;
Ebitani, K.; Kaneda, K. J. Org. Chem. 2000, 65, 6897. (o) Bortolini,
O.; Conte, V.; Chiappe, C.; Fantin, G.; Fogagnolo, M.; Maietti, S.
Green Chem. 2002, 4, 94. (p) Bortolini, O.; Campestrini, S.; Conte,
V.; Fogagnolo, M.; Fantin, G.; Maietti, S. Eur. J. Org. Chem. 2003,
4804. (q) Bortolini, O.; De Nino, A.; Fogagnolo, M.; Fantin, G.;
Mariuolo, L.; Tocci, A. Chem. Lett. 2007, 36, 472.
(3) (a) Darzens, G. C. R. Hebd. Seances Acad. Sci. 1904, 139, 1214.
(b) Darzens, G. C. R. Hebd. Seances Acad. Sci. 1905, 141, 766.
(c) Darzens, G. C. R. Hebd. Seances Acad. Sci. 1906, 142, 214.
(4) For selected reviews on the asymmetric Darzens reaction, see:
(a) Davis, R. L.; Stiller, J.; Naicker, T.; Jiang, H.; Jørgensen, K. A.
Angew. Chem. Int. Ed. 2014, 53, 7406. (b) Bakó, P.; Rapi, Z.;
Keglevich, G. Curr. Org. Synth. 2014, 11, 361.
(5) (a) Bakó, P.; Szöllõsy, Á.; Bombicz, P.; Tõke, L. Synlett 1997, 291.
(b) Bakó, P.; Vízvárdi, K.; Bajor, Z.; Tõke, L. Chem. Commun. 1998,
1193. (c) Bakó, P.; Vízvárdi, K.; Toppet, S.; Van der Eycken, E.;
Hoornaert, G. J.; Tõke, L. Tetrahedron 1998, 54, 14975. (d) Bakó,
P.; Makó, A.; Keglevich, G.; Kubinyi, M.; Pál, K. Tetrahedron:
Asymmetry 2005, 16, 1861.
129.1, 134.0, 135.5, 193.1.
[3-(2-Naphthyl)oxiran-2-yl](phenyl)methanone (3ha)14
White solid; yield: 41.1 mg (0.15 mmol, 51%).
1H NMR (500 MHz, CDCl3): δ = 4.26 (d, J = 1.4 Hz, 1 H), 4.43 (d, J = 1.4
Hz, 1 H), 7.42–7.55 (m, 5 H), 7.63 (t, J = 7.2 Hz, 1 H), 7.85–7.91 (m, 4
H), 8.04 (d, J = 7.7 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 59.6, 61.1, 122.4, 125.9, 126.6, 126.7,
127.8, 127.9, 128.3, 128.8, 128.9, 132.8, 133.0, 133.6, 134.0, 135.4,
193.0.
Phenyl[3-(4-tolyl)oxiran-2-yl]methanone (3ia)12
White solid; yield: 19.1 mg (0.08 mmol, 28%).
1H NMR (400 MHz, CDCl3): δ = 2.39 (s, 3 H), 4.05 (d, J = 1.5 Hz, 1 H),
4.31 (d, J = 1.5 Hz, 1 H), 7.22–7.29 (m, 4 H), 7.50 (dd, J1 = 7.7 Hz, J2 =
7.3 Hz, 2 H), 7.63 (dd, J1 = 7.3 Hz, J2 = 7.7 Hz, 1 H), 8.02 (d, J = 8.2 Hz, 2
H).
13C NMR (100 MHz, CDCl3): δ = 21.3, 59.5, 61.1, 125.8, 128.3, 128.9,
129.4, 132.4, 133.9, 135.5, 139.1, 193.2.
[3-(4-tert-Butylphenyl)oxiran-2-yl](phenyl)methanone (3ja)
Yellow solid; yield: 9.0 mg (0.032 mmol, 11%); mp 71–72 °C.
IR (ATR): 3060, 2963, 2902, 2867, 1688, 1596, 1578, 1510, 1448, 1425,
1392, 1362, 1340, 1311, 1289, 1268, 1224, 1176, 1108, 1072, 1029,
1010, 935, 895, 848, 825, 802, 771, 736, 710, 690, 666, 655 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 1.34 (s, 9 H), 4.06 (d, J = 1.9 Hz, 1 H),
4.33 (d, J = 1.9 Hz, 1 H), 7.32 (d, J = 8.2 Hz, 2 H), 7.44 (d, J = 8.2 Hz, 2 H),
7.50 (t, J = 7.7 Hz, 2 H), 7.62 (t, J = 8.0 Hz, 1 H), 8.02 (d, J = 7.7 Hz, 2 H).
13C NMR (100 MHz, CDCl3): δ = 31.3, 34.7, 59.4, 60.9, 125.6, 125.7,
128.3, 128.9, 132.4, 133.9, 135.5, 152.3, 193.2.
MS (DART): m/z [M + H]+ calcd for C19H21O2: 281.2; found: 281.2.
[3-(4-Bromophenyl)oxiran-2-yl](4-chlorophenyl)methanone
(3ab)15
(6) (a) Arai, S.; Oku, M.; Miura, M.; Shioiri, T. Synlett 1998, 1201.
(b) Arai, S.; Shioiri, T. Tetrahedron Lett. 1998, 39, 2145. (c) Arai,
S.; Ishida, T.; Shioiri, T. Tetrahedron Lett. 1998, 39, 8299. (d) Arai,
S.; Shirai, Y.; Ishida, T.; Shioiri, T. Chem. Commun. 1999, 49.
(e) Arai, S.; Shirai, Y.; Ishida, T.; Shioiri, T. Tetrahedron 1999, 55,
6375. (f) Arai, S.; Shioiri, T. Tetrahedron 2002, 58, 1407. (g) Arai,
S.; Tokumaru, K.; Aoyama, T. Tetrahedron Lett. 2004, 45, 1845.
(7) (a) Sano, S.; Miyamoto, M.; Mitani, T.; Nagao, Y. Heterocycles
2006, 68, 459. (b) Achard, T. J. R.; Belokon, Y. N.; Ilyin, M.;
Moskalenko, M.; North, M.; Pizzato, F. Tetrahedron Lett. 2007,
48, 2965. (c) Guilena, G.; del Carmen Hita, M.; Nájera, C. Tetra-
hedron: Asymmetry 2007, 18, 1272. (d) Liu, W.-J.; Lv, B.-D.;
Gong, L.-Z. Angew. Chem. Int. Ed. 2009, 48, 6503. (e) Liu, G.;
Zhang, D.; Li, J.; Xu, G.; Sun, J. Org. Biomol. Chem. 2013, 11, 900.
White solid; yield: 77.6 mg (0.23 mmol, 78%).
1H NMR (500 MHz, CDCl3): δ = 4.04 (d, J = 1.7 Hz, 1 H), 4.19 (d, J = 1.7
Hz, 1 H), 7.24 (d, J = 8.6 Hz, 2 H), 7.47 (d, J = 8.6 Hz, 2 H), 7.53 (d, J = 8.6
Hz, 2 H), 7.95 (d, J = 8.6 Hz, 2 H).
13C NMR (125 MHz, CDCl3): δ = 58.7, 60.8, 123.1, 127.3, 129.2, 129.7,
131.9, 133.5, 134.3, 140.7, 191.6.
Supporting Information
Supporting information for this article is available online at
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© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–E