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CCDC-743470 (3a )
contains the supplementary crystallographic data for this paper.
More data can be obtained free of charge from The Cambridge Crystallographic
Data Centre via www. ccdc.cam.ac.uk/data_request/cif.
<A NAME="RG32009ST-10">10 </A>
General Procedure
In
an ordinary vial equipped with a magnetic stirring bar, the α,β-unsaturated
aldehyde 1 (2.2 mmol, 2.2 equiv) was dissolved
in CHCl3 (1 mL). The catalyst (S )-2 (0.2 mmol, 0.2 equiv) and nitromethane
(1 mmol, 1 equiv) were added to the solution. The vial was sealed,
and the mixture was stirred for 20 h at r.t. The crude reaction
mixture was diluted in CH2 Cl2 , washed with
H2 O, and dried over MgSO4 . After concentration,
the crude product was purified by flash chromatography (silica gel,
pentane-EtOAc). All new compounds gave satisfactory spectroscopic
and analytical data. As a typical example, the data of the compound 3a are given.
(4
S
,5
R
,6
R
)-5-Nitro-4,6-diphenylcyclohex-1-ene carbaldehyde
(3a, Figure 2)
Isolated as a yellow solid (202 mg,
65%). The ee (>99%) was determined by
HPLC on a chiral stationary phase [Chiralcel OD; n -heptane-i -PrOH
(8:2); 1.0 mL/min, t
R = 9.93
min(major), 18.25 min (minor, based on the racemic mixture)];
mp 108 ˚C; [α]D
²0 -123
(c 1.1, CHCl3 ). IR (ATR):
3060, 2807, 2718, 2323, 2115, 1684, 1653, 1547, 1494, 1450, 1410,
1366, 1247, 1162, 1078, 946 cm-¹ . ¹ H NMR
(400 MHz, CDCl3 ): δ = 2.89
(ddd, J = 5.2,
5.2, 20.0 Hz, 1 H, H3 ); 3.25 (dddd, J = 2.4,
11.2, 11.2, 20.0 Hz, 1 H, H3
′ ), 3.35-3.40
(m, 1 H, H4 ), 4.32-4.38 (m, 1 H, H6 );
4.96 (dd, J = 1.9,
3.0 Hz, 1 H, H5 ), 7.03-7.07 (m, 2 H, HPh-
para
), 7.22-7.38 (m, 9
H, HPh and H2 ), 9.57 (s, 1 H, HCHO ). ¹³ C NMR
(100 MHz, CDCl3 ): δ = 28.0
(C3 ), 37.3 (C4 ), 43.2 (C6 ), 91.3
(C5 ), 127.3 (CH), 128.0 (CH), 128.9 (CH), 129.2 (CH), 137.9,
138.0, 138.8 (CPh , C1 ), 150.4 (C2 ),
191.65 (CHO). HRMS (EI): m/z calcd
for C19 H17 03 N1 : 307.1203;
found: 307.1208.
Figure 2
<A NAME="RG32009ST-11">11 </A>
Trost BM.
Acc.
Chem. Res.
2002,
35:
695