F
J.-L. Zhu, Y.-P. Wu
Letter
Synlett
(11) For the procedure for preparing 1a–d and for the characteriza-
tion of 1a and 1b, see: Molander, G. A.; Cameron, K. O. J. Org.
Chem. 1993, 58, 5931.
(12) 1c is a known compound, see: Schneider, R. A.; Meinwald, J.
J. Am. Chem. Soc. 1967, 89, 2023.
5.4 Hz, 1 H), 1.39 (ddd, J = 13.6, 11.5, 1.8 Hz, 1 H), 1.31–1.20 (m,
1 H), 1.19–1.06 (m, 2 H), 1.06–0.94 (m, 1 H). 13C NMR (100 MHz,
CDCl3): δ = 201.5 (C = O), 119.0 (CN), 46.8, 42.5, 33.9, 30.2, 28.8,
27.4, 25.1, 24.8, 24.7, 23. HRMS (EI): m/z [M]+ calcd for
C
12H15NO: 189.1154; found: 189.1161.
(13) Honda, T.; Sundararajan, C.; Yoshizawa, H.; Su, X.; Honda, Y.;
Liby, K. T.; Spron, M. B.; Gribble, G. W. J. Med. Chem. 2007, 50,
1731.
(19) (a) Doyle, M. P.; Griffin, J. H.; Bagheri, V.; Dorow, R. L. Organo-
metallics 1984, 3, 53. (b) Davies, H. M. L.; Doan, B. D. J. Org.
Chem. 1999, 64, 8501.
(14) Hirayama, T.; Okaniwa, M.; Imada, T.; Ohashi, A.; Ohori, M.;
Iwai, K.; Mori, K.; Kawamoto, T.; Yokota, A.; Tanaka, T.; Ishikawa,
T. Bioorg. Med. Chem. 2013, 21, 5488.
(15) The isomeric mixture of 5 readily decomposed upon prolonged
exposure to deuterated solvents; its 13C NMR spectrum was
therefore not obtained.
(16) Two highly twisted transition conformations have been pro-
posed for producing the possible diastereomers of 5, on the
basis of established theory; see the Supporting Information
and: Taber, D. F.; You, K. K.; Rheingold, A. L. J. Am. Chem. Soc.
1996, 118, 547.
(20) For the characterization of 1e and 1f, see: (a) Biswas, S.; Page, J.
P.; Dewese, K. R.; RajanBabu, T. W. J. Am. Chem. Soc. 2015, 137,
14268. (b) Ohe, T.; Wakita, T.; Motofusa, S.-i.; Cho, C. S.; Ohe, K.;
Uemura, S. Bull. Chem. Soc. Jpn. 2000, 73, 2149.
(21) For the assignment of C-9 and C-10 13C NMR signals of 7a and
7b, see: Condon, S.; Ouarradi, A. E.; Métay, E.; Léonel, E.;
Bourdonneau, M.; Nédélec, J.-Y. Tetrahedron 2008, 64, 9388.
(22) For simplicity, only one of the possible diastereomers of the
norcaradienes is shown in Scheme 10. Besides, the ring opening
and elimination of the proton might also take place in a con-
certed manner.
(17) CCDC 1515037, 1515039, and 1515041 contain the supplemen-
tary crystallographic data for compounds 6, 4b, and 4e. The data
can be obtained free of charge from The Cambridge Crystallo-
(18) (2S*,4aR*,8aS*)-1-Oxodecahydronaphthalene-2-carboni-
trile; Typical Procedure
(23) Rodriguez-Cárdenas, E.; Sabala, R.; Romero-Ortega, M.; Ortiz,
A.; Olivo, H. F. Org. Lett. 2012, 14, 238.
(24) For recent examples, see: (a) Thomas, E. M.; Norman, B. H.;
Kroin, J. S. US 8093302, 2012. (b) Raja, A.; Hong, B.-C.; Lee, G.-H.
Org. Lett. 2014, 16, 5756. (c) Kawaguchi, Y.; Yasuda, S.; Mukai, C.
Angew. Chem. Int. Ed. 2016, 55, 10473.
Rh2(OAc)4 (98%, 0.46 mg, 0.001 mmol) was added to a solution
of diazo nitrile 3a (22.3 mg, 0.1 mmol) in CH2Cl2 (5.1 mL) under
N2, and the resulting suspension was stirred at r.t. for 3 h until a
homogeneous green solution was obtained. The solvent was
then evaporated under reduced pressure, and the residue was
subjected to flash chromatography [silica gel, hexane–EtOAc
(10:1, 5:1, 3:1)] to give 4a as a white solid [yield: 14 mg (72%)],
together with a small amount of 5 [yield: 0.8 mg (4%);
dr = 76:24].
(25) Gao, J.-W. Synlett 2012, 317.
(26) For an example of an electron-promoted ring opening of α-keto
cyclopropanes, see: Stevenson, J. P.; Jackson, W. F.; Tanko, J. M.
J. Am. Chem. Soc. 2002, 124, 4271.
(27) For examples of LN-mediated reductive decyanation, see:
(a) Mattalia, J.-M.; Marchi-Delapierre, C.; Hazimeh, H.; Chanon,
M. ARKIVOC 2006, (iv), 90. (b) Zhu, J.-L.; Huang, P.-W.; You, R.-Y.;
Lee, F.-Y.; Tsao, S.-W.; Chen, I-C. Synthesis 2011, 715.
(28) For examples of the synthetic utility of α-cyano ketones, see:
(a) Yoo, B. W.; Hwang, S. K.; Kim, D. Y.; Choi, J. W.; Ko, J. J.; Choi,
K. I.; Kim, J. H. Tetrahedron Lett. 2002, 43, 4813. (b) Lee, J. H.;
Kim, D. Y. Adv. Synth. Catal. 2009, 351, 1779. (c) Guevara-Pulido,
J. O.; Andrés, J. M.; Pedrosa, R. Eur. J. Org. Chem. 2014, 8072.
(±)-4a: Mp 114–116 °C. IR (neat): 2928, 2856, 2240, 1697 cm–1
.
1H NMR (400 MHz, CDCl3): δ = 2.40–2.32 (m, 1 H), 2.28 (ddd,
J = 13.6, 9.1, 5.8 Hz, 1 H), 1.97–1.90 (m, 1 H), 1.93 (dd, J = 9.3, 5.4
Hz, 1 H), 1.83–1.75 (m, 3 H), 1.73–1.76 (m, 2 H), 1.54 (dd, J = 7.2,
© Georg Thieme Verlag Stuttgart · New York — Synlett 2017, 28, A–F