626
D. Sureshkumar et al. / Tetrahedron Letters 48 (2007) 623–626
1996, 79, 1957–1966; (c) Santi, C.; Wirth, T. Tetrahedron:
Asymmetry 1999, 10, 1019–1023.
(76 MHz, CDCl3): 283.2; HR-ESMS m/z: Calcd for
C32H36N2O4S2Se2[M++Na]: 759.0345. Found: 759.0375.
Compound 6c: Rf = 0.60 (EtOAc/hexanes, 3:7); Yield:
0.120 g, 72%; mp: 121 ꢁC; IR (neat): 3276, 1330, 1160, 816,
6. (a) Nishibayashi, Y.; Singh, J. D.; Segawa, K.; Fukuzawa,
S. I.; Uemera, S. J. Chem. Soc., Chem. Commun. 1994,
1375–1376; (b) Nishibayashi, Y.; Segawa, K.; Singh, J. D.;
Fukuzawa, S. I.; Ohe, K.; Uemura, S. Organometallics
1996, 15, 370–379.
7. Braga, A. L.; Silva, S. J. N.; Luedtke, D. S.; Drekener, R.
L.; Silveira, C. C.; Rocha, J. B. T.; Wessjohann, L. A.
Tetrahedron Lett. 2002, 43, 7329–7331.
670 cmꢁ1 1H NMR (300 MHz, CDCl3, 1:1 mixture of
;
diastereomers): d 7.78 (d, J = 8.4 Hz, 4H), 7.28 (d,
J = 8.4 Hz, 4H), 5.09 (d, J = 9.0 Hz, 1H), 4.85 (d, J =
9.3 Hz, 1H), 3.49–3.39 (m, 2H), 3.24–3.17 (m, 2H), 2.41 (s,
6H), 1.94–1.85 (m, 2H), 1.44 (d, J = 7.2 Hz, 3H), 1.32 (d,
J = 6.9 Hz, 1H), 0.84–0.71 (m, 12H); 13C NMR (75 MHz,
CDCl3, 1:1 mixture of diastereomers): d 143.2, 143.1,
137.8, 137.7, 129.5, 129.4, 127.1, 127.0, 65.0, 64.9, 43.8,
31.6, 31.3, 21.5, 21.0, 20.9, 20.8, 19.0, 18.9; 77Se NMR (76
MHz, CDCl3): 284.2; HR-ESMS m/z: calcd for
C26H40N2O4S2Se2[M++Na]: 691.0658. Found: 691.0680.
13. Crystal data for compound 4c. The structure was solved by
direct methods (SIR92). Refinement was by full-matrix
least-squares procedures on F2 by using SHELXL-97.
Crystal system: Orthorhombic, space group: P212121, cell
8. Sureshkumar, D.; Koutha, S.; Chandrasekaran, S. J. Am.
Chem. Soc. 2005, 127, 12760–12761.
9. (a) Saravanan, V.; Porhiel, E.; Chandrasekaran, S. Tetra-
hedron Lett. 2003, 44, 2257–2260; (b) Bhat, R. G.; Porhiel,
E.; Saravanan, V.; Chandrasekaran, S. Tetrahedron Lett.
2003, 44, 5251–5253; (c) O’ Neal, S.; Kollis, J. W. J. Am.
Chem. Soc. 1998, 110, 1971–1973; (d) Muller, A.; Die-
mann, E.; Jostes, R.; Bogge, H. Angew. Chem. 1981, 93,
957–977.
10. Iwaoka, M.; Tomoda, S. Top. Curr. Chem. 2000, 55, 208.
11. (a) Bates, G. S.; Varelas, M. A. Can. J. Chem. 1980, 58,
2562–2566; (b) Lohray, B. B.; Gao, Y.; Sharpless, K. B.
Tetrahedron Lett. 1989, 30, 2623–2626; (c) Berry, M. B.;
Craig, D. Synlett 1992, 41–44; (d) Bieber, L. W.; De
Araujo, M. C. F. Molecules 2002, 7, 902–906.
12. General procedure for aziridine ring opening with 1: To a
stirred solution of aziridine 3g (0.144 g, 0.5 mmol) in
CH2Cl2 (3 mL), tetraethylammonium tetraselenotungstate
1 (0.455 g, 0.60 mmol) was added at room temperature
(28 ꢁC). After completion of the reaction (TLC, 2 h) the
solvent was removed in vacuo and the black residue was
extracted with CH2Cl2–Et2O (1:4, 5 · 20 mL) and filtered
through a Celite pad. The filtrate was concentrated and
the crude product was purified by flash column chroma-
tography on silica gel (230-400 mesh, eluting with
hexane:ethyl acetate 9:1) to obtain the b-aminodiselenide
4g as a yellow oil.
˚
parameters: a = 13.041(3), b = 14.234(3), c = 18.824(4) A,
3
˚
a = 90.00, b = 90.00, c = 90.00ꢁ, V = 3494.32 A , Z = 4,
q
calcd = 1.27 g cmꢁ3, F(000) = 1368, l = 2.26 mmꢁ1, k =
˚
0.71073 A. Total number l.s. parameters = 331. R1 =
0.058 for 6156 F0 > 4r(F0) and 0.095 for all 25,458 data.
wR2 = 0.121, GOF = 0.984, restrained GOF = 0.984 for
all data. (CCDC 610612). Crystallographic data (exclud-
ing structure factors) for the structure in this letter have
been deposited with the Cambridge Crystallographic Data
Centre as a supplementary publication. Copies of these
data can be obtained, free of charge, on application to
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; fax:
+44 1223 336033 or e-mail: deposit@ccdc.cam.ac.uk or
14. Iwamoto, K.; Kajima, M.; Chatani, N.; Murai, S. J. Org.
Chem. 2001, 66, 169–174.
15. Jeong, J. U.; Tao, B.; Sagasser, I.; Henniges, H.; Sharp-
less, K. B. J. Am. Chem. Soc. 1998, 120, 6844–6845.
16. (a) Kruhlak, N. L.; Wang, M.; Boorman, P. M.; Parvez,
M. Inorg. Chem. 2001, 40, 3141–3148; (b) Boorman, P. M.;
Wang, M.; Parvez, M. J. Chem. Soc., Chem. Commun.
1995, 999–1000; (c) Pan, W. H.; Harmer, M. A.; Halbert,
T. R.; Stiefel, E. I. J. Am. Chem. Soc. 1984, 106, 459–460;
(d) Coyle, C. L.; Harmer, M. A.; George, G. N.; Daage,
M.; Stiefel, E. I. Inorg. Chem. 1990, 29, 14–19, and
references cited therein; (e) Prabhu, K. R.; Sivanand, P.;
Chandrasekaran, S. Angew. Chem., Int. Ed. 2000, 39,
4316–4319.
Compound 4g: Rf = 0.65 (EtOAc/hexanes, 3:7); Yield:
27
0.156 g, 85%; ½aꢀD ꢁ75.22 (c 4.6, CH2Cl2); IR (neat): 3280,
1333, 1157, 1090, 1035, 814, 667 cmꢁ1
;
1H NMR
(300 MHz, CDCl3): d 7.61 (d, J = 8.1 Hz, 4H), 7.19–7.16
(m, 10H), 6.98–6.95 (m, 4H), 5.13 (d, J = 7.5 Hz, 2H),
3.74–3.65 (m, 2H), 3.23 (dd, J = 12.6, 4.8 Hz, 2H), 3.01
(dd, J = 12.6, 6.6 Hz, 2H), 2.87 (dd, J = 14.0, 6.3, 2H),
2.70 (dd, J = 14.0, 6.9 Hz, 2H), 2.39 (s, 6H); 13C NMR
(75 MHz, CDCl3): d 143.2, 137.0, 136.4, 129.6, 129.3,
128.6, 126.9, 126.7, 55.4, 39.9, 35.5, 21.5; 77Se NMR