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19. All new compounds gave satisfactory physical, analytical,
and spectroscopic data. Typical procedure for the synthesis of
18: A mixture of 14e (0.08 mmol, 19.6 mg) and 3-pentanone
(4 mmol, 423 lL) in NMP (0.2 mL) was stirred for 20 min at
rt. Then, trans-4-chloro-b-nitrostyrene (0.4 mmol, 73.4 mg)
was added and the mixture was stirred for 4 days. The
reaction was extracted with EtOAc (3 · 5 mL), dried over
Na2SO4, filtered, and the solvent evaporated. The residue was
purified by flash chromatography (hexane/AcOEt: 12/1) to
afford pure 18. The catalyst was recovered from the column
with AcOEt/MeOH: 2/1 (15.8 g, 80% recovery). Selected data
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20
for 18: ½aꢀD ¼ þ5:7 (c 1.0, CH2Cl2) for 78% ee; Rf 0.2
(hexane/AcOEt: 5/1); IR (KBr) m 1553 (NO2), 1711 (C@O)
(g) Xu, Y.; Cordova, A. Chem. Commun. 2006, 460–462; (h)
cmꢁ1 1H NMR (CDCl3, 400 MHz): d 0.96 (d, J = 7.1 Hz,
;
´
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Tetrahedron: Asymmetry 2006, 17, 491–493.
3H, CH3CH), 1.07 (t, J = 7.1 Hz, 3H, CH3CH2), 2.41, 2.62
(2dq, J = 17.9, 7.1 Hz, 2H, CH3CH2), 2.95 (dq, J = 9.3,
7.2 Hz, 1H, CH3CH), 3.69 (dt, J = 9.3, 4.9 Hz, 1H,
CHCH2N), 4.58 (dd, J = 12.4, 4.8 Hz, 1HxCH2NO2), 4.64
(dd, J = 12.4, 9.0 Hz, 1Hx CH2NO2), 7.11 (d, J = 8.3 Hz, 2H,
ArH), 7.31 (dd, J = 6.6 Hz, 2H, HAr); 13C NMR (CDCl3,
100 MHz): d 7.6 (CH3CH2), 16.2 (CH3CH), 35.4 (CH2CH3),
45.4 (CHCH2N), 48.1 (CHCH3), 78.0 (CH2NO2), 129.2,
129.3, 133.8, 136.0 (ArC), 213.1 (C@O); m/z (EI) 269
(M+ꢁ29, <1%), 193 (19), 138 (18), 115 (10), 57 (100). HRMS
calcd for C13H16ClNO3 = 269.0819, (M+ꢁNO2) 223.0884,
found 223.0874. HPLC (Chiralcel OD-H, 1 mL/min, 99:1
hexane/IPA, k = 210 nm), retention time 22.6 min (major)/
25.8 min (minor).
9. For the organocatalytic asymmetric Michael addition of 1,3-
dicarbonyl compounds to nitro olefins, see: Terada, M.; Ube,
H.; Yaguchi, Y. J. Am. Chem. Soc. 2006, 128, 1454–1455, and
references cited therein.
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