3482
B. B. Semenov et al. / Tetrahedron Letters 47 (2006) 3479–3483
Table 3. Characteristic 1H and C NMR chemical shifts for (R*,S*,S*), (R*,S*,R*), (R*,R*,R*), (R*,R*,S*) 2-1H-indol-3-yl(phenyl)methyl]-2,3-
13
dihydro-1H-inden-1-ols (5 and 8)
H
H
O
H
O
H
O
O
1'
1'
1'
1'
1
1
1
1
2
2
2
2
3
3
3
3
N
H
N
H
N
H
N
H
R*,S*,R*
R*,S*,S*
R*,R*,R*
R*,R*,S*
Atom no.
R*S*S*
R*S*R*
1H
4.14
4.80
5.15
3.16
3.02, 2.45
10.86
13C
1H
4.52
4.44
4.63
3.22
13C
1
45.4
78.8
—
52.9
34.9
—
42.2
73.9
—
50.0
36.4
—
10
10(OH)
2
3
NH
2.70, 2.24
10.80
Atom no.
R*R*R*/R*R*S*
R*R*S*/R*R*R*
1H
13C
1H
13C
1
4.45
4.85
4.56
42.2
74.1
—
4.14
4.74
4.87
46.1
78.4
—
10
10(OH)
2
3
NH
3.15
2.71, 2.24
10.77
49.8
36.4
—
3.14
3.15, 2.60
10.86
53.0
35.9
—
11. Seebach, D.; Prelog, V. Angew. Chem., Int. Ed. Engl. 1982,
94, 696.
References and notes
12. Mislow, K.; Siegel, J. J. Am. Chem. Soc. 1984, 106, 3319–
3328.
1. Prelog, V. Helv. Chem. Acta 1953, 36, 308.
2. Ruch, E.; Ugi, I. Top. Stereochem. 1969, 4, 99.
3. A 33% solution of methylamine (150 g, 1.59 mol) was
added over 20 min to a solution of benzaldehyde (106 g,
1 mol). Mixing was accompanied by considerable heat
evolution. In order to complete the reaction, the mixture
was kept for 12 h at ꢀ20 °C. The mixture was saturated
with sodium chloride and extracted with ether. The
ethereal extract was dried (MgSO4) and then the ether
distilled off. The residue was distilled to give benzalmeth-
ylamine (83 g, 70%). Bp 183–185 °C. (Literature data: bp
92–93 °C at 34 mm).18 A solution of indole (30 g, 0.26
mol) in benzalmethylamine (36 g, 0.30 mol) was heated for
40 h at 70 °C. The mixture was then kept at room
temperature until complete crystallisation occurred. The
resulting precipitate was filtered off and recrystallised from
benzene giving white crystals that turned pink in air
(49 g, 65%). Mp 139–141 °C. (Literature data: mp 139–
141 °C).19
13. A solution of a base (0.1 g) in H2O (1 ml) and 1-indanone
(0.625 mmol) was added to a boiling solution of a-phenyl-
nor-gramine 1 (1.0 g, 0.42 mmol) in ethanol (90%, 10 ml);
the mixture was refluxed under a stream of an argon until
the starting material was consumed (TLC ethyl acetate–
CCl4, 1:4). The reaction mixture was cooled to room
temperature and the resulting precipitate filtered off. Yield
21
45%, mp 247 °C. In the case of chiral catalysts, ½aꢁD +0.5
(c 2, DMSO).
14. X-ray diffraction analysis: at 120 K, the crystals of
4 (C24H19NO) are monoclinic, space group C2/c, a =
˚
24.044(3), b = 6.3355(8), c = 25.451(3) A, b = 115.060(3)°,
3
V = 3512.0(8) A , Z = 8 (Z0 = 1), M = 337.40, dcalc
=
˚
1.276 g cmꢂ3, l(MoKa) = 0.77 cmꢂ1, F(000) = 1424. Inten-
sities of 7420 reflections were measured at 120 K with a
Smart 1000 CCD diffractometer (k(MoKa) = 0.71072 A,
2h < 52°), and 3423 independent reflections (Rint = 0.0701)
were used in the further refinement. The structure was solved
by a direct method and refined by the full-matrix least-
squares technique against F2 in the anisotropic–isotropic
approximation. The hydrogen atoms were located from the
Fourier density synthesis. The refinement converged to
wR2 = 0.1532 and GOF = 0.938 for all independent reflec-
tions (R1 = 0.0581 was calculated against F for 1393
observed reflections with I > 2r(I)). All calculations were
performed using SHELXTL PLUS 5.0. Crystallographic data
(excluding structure factors) for the structures reported in
this letter have been deposited with the Cambridge Crystal-
lographic Data Centre as supplementary no. 291553. Copies
of the data can be obtained free of charge on application to
CCDC, 12 Union Road, Cambridge CB2 1EZ UK (Fax:
(internat.) +44-1223/336-033; E-mail: deposit@ccdc.cam.
ac.uk).
4. Semenov, B. B.; Smushkevich, Yu. I.; Grintselev-Knyazev,
G. V.; Antipin, M. Yu. Izv. AN., Ser. Khim. 2001, 3, 543–
545.
5. Semenov, B. B.; Smushkevich, Yu. I.; Levina, I. I.;
Kurkovskaya, L. N.; Lysenko, K. A.; Kachala, V. V.
Khim. Geterotsikl. Soedin. 2005, 848–857.
6. Semenov, B. B. Ph.D. Dissertation, D. I. Mendeleev
University of Chemical Technology, 2002.
7. Semenov, B. B.; Yurovskaya, M. A. Preparative Chemistry
of Gramines; Companiya Sputnik+: Moscow, 2005 (in
Russian).
8. Snyder, H. J. Am. Chem. Soc. 1957, 79, 2217–2221.
9. Aitken, R.; Kilenyi, S. N. Asymmetric Synthesis; Chapman
& Hall: New York, 1992.
10. Prelog, V.; Helmchen, G. Angew. Chem., Int. Ed. Engl.
1982, 94, 614.