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Russ.Chem.Bull., Int.Ed., Vol. 62, No. 4, April, 2013
Kucherenko et al.
C, 67.13; H, 10.52; N, 10.44. 1H NMR (CDCl3), : 0.88 (d, 3 H,
J = 7.3 Hz); 1.02 (d, 3 H, J = 7.3 Hz); 1.09 (s, 3 H); 1.30 (s, 6 H);
1.39—1.55 (m, 2 H); 1.60—1.83 (s, 2 H); 1.91—2.04 (m, 2 H);
2.19—2.33 (m, 2 H); 2.47—2.59 (m, 1 H); 3.22 (d, 1 H,
J = 5.1 Hz); 4.36 (q, 1 H, J = 7.1 Hz); 7.62 (d, 1 H, J = 6.2 Hz).
13C NMR (CDCl3), : 16.73, 19.61, 23.69, 28.24, 28.81, 29.88,
31.47, 36.26, 38.81, 40.67, 47.95, 54.77, 60.81, 74.21, 173.85.
(S)ꢀ2ꢀAminoꢀ3ꢀmethylꢀNꢀ[1ꢀ(S)ꢀphenylethyl]butanamide
(1m). The yield was 96%, m.p. 52—53 C; []20D +52.20 (c 1.0,
CHCl3). Found (%): C, 70.75; H, 9.24; N, 12.66. C13H20N2O.
C, 70.87; H, 9.15; N, 12.72. 1H NMR (CDCl3), : 0.85 (d, 3 H,
J = 7.3 Hz); 0.98 (d, 3 H, J = 7.3 Hz); 1.50 (d, 3 H, J = 7.0 Hz);
1.57 (s, 2 H); 2.30 (m, 1 H); 3.22 (d, 1 H, J = 3.7 Hz); 5.13
(m, 1 H); 7.17—7.40 (m, 5 H); 7.64 (s, 1 H). 13C NMR (CDCl3),
: 16.0, 19.5, 21.9, 30.8, 48.1, 59.9, 126.0 (2 C), 127.0, 128.4
(2 C), 143.4, 173.2.
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(1n). The yield was 94%, m.p. 56—57 C; []20 –88.2 (c 1.0,
D
CHCl3). Found (%): C, 70.78; H, 9.22; N, 12.62. C13H20N2O.
Calculated (%): C, 70.87; H, 9.15; N, 12.72. 1H NMR (CDCl3),
: 0.75 (d, 3 H, J = 7.0 Hz); 0.95 (d, 3 H, J = 7.0 Hz); 1.48
(d, 3 H, J = 6.6 Hz); 1.72 (s, 2 H); 2.25 (m, 1 H); 3.25 (d, 1 H,
J = 3.7 Hz); 5.14 (m, 1 H); 7.15—7.42 (m, 5 H); 7.60 (s, 1 H).
13C NMR (CDCl3), : 16.0, 19.5, 21.9, 30.8, 40.1, 59.9, 125.9
(2 C), 126.9, 128.4 (2 C), 143.5, 173.3.
Aldol reactions (general procedure). A mixture of catalyst 1
(0.05 mmol), ketone 4 (0.80 mmol), aldehyde 5 (0.26 mmol),
and water (0.5 mL) was stirred at room temperature for the time
specified in Tables 1 and 2 (TLC monitoring). The reaction
mixture was extracted with Et2O (2×5 mL), the extracts were
filtered through the silica gel pad (1.0 g), the solvent was evapoꢀ
rated (15 Torr). The ratio of synꢀ and antiꢀ aldols 6 was deterꢀ
mined from the 1H NMR spectra of crude reaction mixture. The
mixtures of synꢀ and antiꢀisomers of aldols 6 were purified on
a column with silica gel (eluent hexane—ethyl acetate (3 : 1)).
1H NMR spectra of known compounds 6a—i corresponded to
the literature data.27—29 The ee values of antiꢀ and synꢀisomers 6
were determined by HPLC on Chiralcel ODꢀH, OJꢀH, or AD
chiral phases.
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This work was financially supported in parts by the
Council on Grants at the President of the Russian Federaꢀ
tion (Program of State Support for Young ScientistsꢀCanꢀ
didates of Science, Grant MKꢀ3551.2012.3), the Russian
Academy of Sciences (Program of Basic Research of
the Presidium of RAS Pꢀ08), and the Russian Foundaꢀ
tion for Basic Research (Project Nos 12ꢀ03ꢀ00420 and
12ꢀ03ꢀ31805).
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