1326
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 6, June, 2004
Dvornikova et al.
(
(
CDCl ), δ: 22.78 (C(9)); 27.18 (C(8)); 27.96 (C(7)); 28.24
C(10)); 33.53 (C(4)); 38.18 (C(5)); 38.27 (C(6)); 50.40 (C(1));
References
3
5
1.22 (C(11)); 76.13 (C(2)); 176.33 (C(3)).
1S,2S,5S)ꢀ3ꢀ[{2ꢀ[(2ꢀHydroxybenzylidene)amino]ethyl}imiꢀ
1. E. N. Jacobsen, W. Zhang, A. R. Muci, J. R. Ecker, and
L. Deng, J. Am. Chem. Soc., 1991, 113, 7063.
2. Y. N. Ito and T. Katsuki, Bull. Chem. Soc. Jpn., 1999, 72, 603.
3. C. Kokubo and T. Katsuki, Tetrahedron, 1996, 52, 13895.
4. W. Adam, R. T. Fell, V. R. Stegmann, and C. R. Sahaꢀ
Moller, J. Am. Chem. Soc., 1998, 120, 708.
(
no]ꢀ2,6,6ꢀtrimethylbicyclo[3.1.1]heptanꢀ2ꢀol (5). A solution
of monoimine 3 (2.0 g, 9.51 mmol) and salicylaldehyde (1.2 g,
9
.51 mmol) in anhydrous MeOH (30 mL) was stirred at ~20 °C
for 4 h. After removal of the solvent in vacuo, the residue was
recrystallized from an Et O—hexane mixture. The yellow
crystals that precipitated were filtered off and washed with
5. T. Fukuda and T. Katsuki, Tetrahedron, 1997, 53, 7201.
6. Y. N. Belokon, N. S. Ikonnikov, M. Moscalenko, M. North,
S. Orlova, V. Tararov, and L. Yashkina, Tetrahedron Asymꢀ
metry, 1996, 7, 851.
2
hexane. Dioxydiimine 5 was obtained in a yield of 2.78 g
0
(
93%), m.p. 97—98 °C, [α]2
+78.5 (c 1.02, EtOH).
D
Found (%): C, 72.52; H, 7.94; N, 8.83. C H N O . Calꢀ
7. Y. N. Belokon, M. North, and T. Parsons, Org. Lett., 2000,
2, 1617.
8. S. E. Schaus, J. Branalt, and E. N. Jacobsen, J. Org. Chem.,
1998, 63, 403.
1
9
26
2
2
–
1
culated (%): C, 72.58; H, 8.34; N, 8.91. IR, ν/cm : 3276 (OH);
1
1
1
638, 1658 (C=N). H NMR (CDCl ), δ: 0.66 (s, 3 H, Me);
3
.26 (s, 3 H, Me); 1.40 (s, 3 H, Me); 1.44 (d, 1 H, H (7),
β
J = 10.6 Hz); 1.99 (m, 2 H, H (7) and H(1)); 2.27 (m, 1 H,
9. K. Aikawa, R. Irie, and T. Katsuki, Tetrahedron, 2001,
57, 845.
α
H(5)); 2.49 (m, 2 H, H C(4)); 2.63 (br.s, 1 H, HOCMe);
2
3
6
.59—3.67 (m, 2 H, C(12)H ); 3.88—3.99 (m, 2 H, C(11)H );
10. Y. N. Belokon, M. North, T. D. Churkina, N. S. Ikonnikov,
and V. I. Maleev, Tetrahedron, 2001, 57, 2491.
11. J. Lopez, S. Liang, and X. R. Bu, Tetrahedron Lett., 1998,
39, 4199.
12. G.ꢀJ. Kim and J.ꢀH. Shin, Catal. Lett., 1999, 63, 83.
13. P. Pietikainen and A. Haikarainen, J. Mol. Catal. A: Chemiꢀ
cal, 2002, 180, 59.
2
2
.83—6.93 and 7.21—7.30 (both m, 4 H, Ar); 8.33 (s, 1 H,
1
3
H(13)); 13.48 (br.s, 1 H, HO—Ar). C NMR (CDCl ), δ:
3
2
3
5
1
1
2.57 (C(9)); 27.23 (C(8)); 28.01 (C(7)); 28.33 (C(10));
3.71 (C(4)); 38.29 (C(5) and C(6)); 50.22 (C(1));
0.53 (C(11)); 59.72 (C(12)); 76.41 (C(2)); 116.95 (C(16));
18.42 (C(18)); 118.64 (C(14)); 131.17 (C(17)); 132.15 (C(19));
66.03 (C(13)).
14. A. H. M. de Vries, R. Imbos, and B. L. Feringa, Tetrahedron
Asymmetry, 1997, 8, 1467.
Xꢀray diffraction analysis of compound 5. Xꢀray data
were collected on an automated EnrafꢀNonius CAD 4
diffractometer at ~20 °C (MoꢀKα radiation, λ = 0.71073 Å,
15. P. A. Petukhov, S. N. Bizyaev, and A. V. Tkachev, Izv.
Akad. Nauk, Ser. Khim., 2001, 2013 [Russ. Chem. Bull., Int.
Ed., 2001, 50, 2106 (Engl. Transl.)].
graphite monochromator). Crystals of
5 (C19H26N O ,
2 2
M
= 314.42) are orthorhombic, space group Р2 2 2 ,
16. A. G. Tolstikov, O. V. Tolstikova, T. B. Khlebnikova, and
N. N. Karpyshev, Khimiya i komp´yuternoe modelirovanie.
Butlerovskie soobshcheniya 2002, 1 [Chemistry and Comꢀ
puter Simulation. Butlerov Communications, 2002, 1 (Engl.
Transl.)].
1
1 1
3
a = 11.420(4), b = 14.097(5), c = 22.259(8) Å, V = 3583(2) Å ,
Z = 8, dcalc = 1.166 g cm–3, µ(MoꢀKα ) = 0.076 mm
F(000) = 1360. A total of 6676 reflections were measured (of
which 5283 reflections are independent, Rint = 0.0171) using the
ωꢀscanning technique in the range 2.00 < θ < 24.98° (–13 < h < 2,
–1
,
17. N. Irako, Y. Hamada, and T. Shioiri, Tetrahedron, 1995,
51, 12731.
–
16 < k < 3, –26 < l < 5). The intensities of reflections were
2
1
corrected for the Lorentz and polarization factors. Absorption
was ignored. The structure was solved by direct methods
18. R. M. Sultanova, M. D. Khanova, I. A. Dvodnikova, A. V.
Kuchin, V. A. Dokichev, Yu. V. Tomilov, and O. M.
Nefedov, Abstrs. of Papers, VII Conf. on the Chemistry of
Carbenes and Related Intermediates (Kazan, June 23—26,
2003), p. 40.
2
2
(
SHELXꢀ86 ). All nonhydrogen atoms were refined anisotroꢀ
2
pically by the fullꢀmatrix leastꢀsquares method against F
2
3
(
SHELXLꢀ97 ). All hydrogen atoms, except for H(11), H(12),
H(21), and H(22), were placed in calculated positions; four
hydroxy H atoms were revealed from difference electron density
syntheses. All hydrogen atoms were refined isotropically. The
final reliability factors were R = 0.0291 and wR = 0.0674 for
19. S. W. Markowicz, K. Pokrzeptowicz, J. Karolakꢀ
Wojciechowska, R. Czylkowski, J. Omelanczuk, and
A. Sobczak, Tetrahedron Asymmetry, 2002, 13, 1981.
20. R. G. Carlson and J. K. Pierce, J. Org. Chem., 1971, 36, 2319.
21. K. Harms, XCAD4. Program for the LpꢀCorrection of Nonius
CAD 4 Data, Marburg, 1997.
1
2
3
143 reflections with I > 2σ (I ); 624 parameters were refined;
GOOF = 0.977.
2
2
2. G. M. Sheldrick, Acta Crystallogr., Sect. A, 1990, 46, 467.
3. G. M. Sheldrick, SHELXLꢀ97. Program for the Refinement of
Crystal Structures, Göttingen University, Göttingen, 1997.
This study was financially supported by the Internaꢀ
tional Science and Technology Center (ISTC, Grant 99ꢀ
1
541) and the Russian Foundation for Basic Research
Received September 5, 2003;
(
Project Nos. 00ꢀ03ꢀ40139 and 01ꢀ03ꢀ32474).
in revised form January 20, 2004