E
T. F. Mabasa et al.
Letter
Synlett
25, 2938. (g) Grossman, O.; Gelman, D. Org. Lett. 2006, 8, 1189.
(h) Weissman, S. A.; Zewge, D.; Chen, C. J. Org. Chem. 2005, 70,
1508. (i) Qi, C.; Hu, X.; He, H. Synlett 2016, 27, 1979.
(j) Chatterjee, T.; Dey, R.; Ranu, B. C. J. Org. Chem. 2014, 79,
5875. (k) Yu, H.; Richey, R. N.; Miller, W. D.; Xu, J.; May, S. A.
J. Org. Chem. 2011, 76, 665. (l) Littke, A.; Soumeillant, M.;
Kaltenbach, R. F. III.; Cherney, R. J.; Tarby, C. M.; Kiau, S. Org. Lett.
2007, 9, 1711. (m) Zanon, J.; Klapars, A.; Buchwald, S. L. J. Am.
Chem. Soc. 2003, 125, 2890. (n) Cheng, Y.-n.; Duan, Z.; Li, T.; Wu,
Y. Synlett 2007, 543. (o) Gan, Y.; Wang, G.; Xie, X.; Liu, Y. J. Org.
Chem. 2018, 83, 14036. (p) Takise, R.; Itami, K.; Yamaguchi, J.
Org. Lett. 2016, 18, 4428. (q) Heravi, M. M.; Panahi, F.; Iranpoor,
N. Org. Lett. 2018, 20, 2753.
(24) Kinfe, H. H. Org. Biomol. Chem. 2019, 17, 4153.
(25) Malinowski, M.; Tran, T. V.; de Robichon, M.; Lubin-Germain, N.;
Ferry, A. Adv. Synth. Catal. 2020, 362, 1.
(26) Hall, R. H.; Jordaan, A. J. Chem. Soc., Perkin Trans. 1 1973, 1059.
(27) CCDC 1969200 (2d) and 1969201 (3) contain the supplemen-
tary crystallographic data for this paper. The data can be
obtained free of charge from The Cambridge Crystallographic
(28) Typical procedure: A solution of pre-prepared aldoxime 1a
(100 mg, 0.218 mmol) in AcOH/Ac2O (1:1.75, 2 mL) in a 10 mL
round-bottom flask fitted with a condenser was heated at
110 °C for 4 h under a nitrogen atmosphere. The reaction
mixture was then allowed to cool to room temperature and 15%
aq. NaOH was added until the solution became slightly basic.
The resultant mixture was extracted with ethyl acetate and the
combined organic phases were washed successively with satu-
rated bicarbonate, brine and water, dried over MgSO4 and con-
centrated to dryness. The residue product was purified by
column chromatography on silica gel using a mixture of ethyl
acetate/hexane (9:1) as eluent to provide 2-cyanoglucal 2a in
72% yield.
(13) Yang, S. H.; Chang, S. Org. Lett. 2001, 3, 4209.
(14) Li, D.; Shi, F.; Guo, S.; Deng, Y. Tetrahedron Lett. 2005, 46, 671.
(15) Yadav, L. D. S.; Srivastava, V. P.; Patel, R. Tetrahedron Lett. 2009,
50, 5532.
(16) Kim, H. S.; Kim, S. H.; Kim, J. N. Tetrahedron Lett. 2009, 50, 1717.
(17) Enthaler, S.; Weidauer, M.; Schröder, F. Tetrahedron Lett. 2012,
53, 882.
(18) Ma, X.-Y.; He, Y.; Lu, T.-T.; Lu, M. Tetrahedron 2013, 69, 2560.
(19) Ghosh, P.; Subba, R. Tetrahedron Lett. 2013, 54, 4885.
(20) Ghosh, P.; Saha, B.; Pariyar, G. C.; Tamang, A.; Subba, R. Tetrahe-
dron Lett. 2016, 57, 3618.
(21) Leggio, A.; Belsito, E. L.; Gallo, S.; Liguori, A. Tetrahedron Lett.
2017, 58, 1512.
(22) (a) Hauser, C. R.; Jordan, E. J. Am. Chem. Soc. 1935, 57, 2450.
(b) Mowry, D. T.; Morner, R. R. J. Am. Chem. Soc. 1947, 69, 1831.
(c) Browne, M. F.; Shriner, R. L. J. Org. Chem. 1957, 22, 1320.
(d) Anderson, H. J. Can. J. Chem. 1959, 37, 2053. (e) Anderson, H.
J. Can. J. Chem. 1968, 46, 798. (f) Song, Y.; Shen, D.; Zhang, Q.;
Chen, B.; Xu, G. Tetrahedron Lett. 2014, 55, 639.
Compound 2a: Yield: 72%; colorless oil. IR (neat): 2214.3 cm–1
(C≡N). HRMS: m/z [M + Na]+ calcd: 441.1940; found: 441.1835.
1H NMR (CDCl3, 400 MHz): = 7.40–7.23 (m, 15 H, Ar), 7.15 (s,
1 H, H1), 4.78 (d, J = 11.5 Hz, 1 H, -CH1aPh), 4.70–4.55 (m, 3 H,
-CH2Ph and -CH1bPh), 4.50 (s, 2 H, -CH2Ph), 4.39 (q, J = 14.8 Hz,
1 H, H5), 4.14 (d, J = 4.8 Hz, 1 H, H3), 3.86 (t, J = 10.4 Hz, 1 H,
H4), 3.77 (dd, J = 6.0, 11.0 Hz, 1 H, H6a), 3.68 (dd, J = 3.5, 14.5 Hz,
1 H, H6b). 13C NMR (100 MHz, CDCl3): = 157.0 (C1), 137.5,
137.2, 137.1, 128.6, 128.5, 128.4, 128.2, 128.1, 128.06, 128.0,
127.9, 127.8, 127.7 (Ar), 117.9 (C2), 89.1 (CCN), 77.9 (C5), 73.5,
73.1, 72.6 (CH2Ph×3), 71.9 (C3 and C4), 67.5 (C6).
(23) Moshapo, P. T.; Mokela, S.; Mmutlane, E. M.; Mampa, R. M.;
Kinfe, H. H. Org. Biomol. Chem. 2016, 14, 5627.
(29) Booma, C.; Balasubramanian, K. K. J. Chem. Soc., Perkin Trans. 1
1993, 393.
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