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DOI: 10.1055/s-0029-1217380
Asymmetric Synthesis of Functionalized 3,4-Dihydronaphthalenes via an Organocatalytic Domino Nitroalkane-Michael/Aldol Condensation Reaction
Publikationsverlauf
Publikationsdatum:
15. Juni 2009 (online)
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Abstract
An organocatalytic domino nitroalkane-Michael addition/aldol condensation reaction has been developed. This process provides an efficient asymmetric synthesis of trisubstituted 3,4-dihydronaphthalenes in moderate to good yields (40-75%) and high stereoselectivities (de >98%, ee = 91 to >99%).
Key words
dihydronaphthalenes - organocatalysis - domino reaction - Michael addition - aldol condensation
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References and Notes
Compound 3c: CCDC-725063 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallo-graphic Data Centre via www.ccdc.cam.ac.uk/data_request/cif
13
General Procedure:
To a solution of 2-(nitromethyl)-benzaldehyde (1;
1.0 mmol) and α,β-unsatured aldehyde
2 (1.1 mmol, 1.1 equiv) in Et2O
(2 mL), was added (S)-di-phenylprolinol
TMS-ether [(S)-4;
0.05 mmol, 5 mol%]. The reaction mixture was stirred
at the temperature and for the time displayed in Table
[²]
.
Workup A: Direct
purification of the reaction mixture by flash chromatography afforded
3,4-dihydronaphthalenes 3 (pentane-Et2O,
2-10:1).
Workup B: Direct suction through a funnel
followed by washing with Et2O afforded 3c.
Workup
C: The reaction mixture was suctioned through a funnel and washed
with Et2O. Purification of the obtained solid by flash
chromatography (silica gel, pentane-Et2O, 1:3)
afforded 3d.
(3
R
,4
S
)-3-(2-Methoxyphenyl)-4-nitro-3,4-dihydro-naphthalene-2-carbaldehyde
(3c; Figure 2): Isolated as a colorless solid (206 mg, 67%).
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
= 9.04 min(major),
10.29 min (minor, based on the racemic mixture)]; mp 182 ˚C; [α]D
²0 -482
(c 1.0, CHCl3); IR (KBr): 3310
(w), 3000 (w), 2946 (w), 2823 (m), 2728 (w), 2324 (w), 2268 (w),
2184 (w), 2048 (w), 1989 (w), 1942 (w), 1735 (w), 1701 (w), 1663
(vs), 1627 (s), 1599 (m), 1570 (m), 1538 (vs), 1489 (s), 1460 (s),
1435 (m), 1399 (s), 1358 (s), 1327 (m), 1289 (s), 1273 (s), 1245
(vs), 1192 (w), 1158 (vs), 1105 (s), 1052 (s), 1028 (s), 961 (w),
924 (s), 855 (m), 819 (m), 755 (vs), 704 (s) cm-¹; ¹H
NMR (400 MHz, CDCl3): δ = 3.95 (s,
3 H, OCH3), 5.48 (br s, J = <2
Hz, 1 H, H-3), 5.62 (br s, J = <2
Hz, 1 H, H-4), 6.60 (dd, J = 7.6,
1.6 Hz, 1 H, H-6′), 6.65 (td, J = 7.6, 0.8 Hz,
1 H, H-5′), 6.91 (d, J = 7.6
Hz, 1 H, H-3′), 7.19 (td, J = 7.6,
1.6 Hz, 1 H, H-4′), 7.36-7.42
(m, 2 H, H-5,7), 7.48-7.54 (m, 2 H, H-6,8),
7.68 (s, 1 H, H-1), 9.73 (s, 1 H, CHO); ¹³C
NMR (101 MHz, CDCl3): δ = 34.5 (C-3),
55.6 (OCH3), 86.4 (C-4), 110.8 (C-3′), 120.3
(C-5′), 122.5 (C-1′), 126.9 (C-6′), 128.0
(C-9), 129.0 (C-4′), 129.4 (C-8), 130.9 (C-6), 131.3 (C-5),
131.6 (C-7), 131.7 (C-10), 137.8 (C-2), 144.1 (C-1), 156.7 (C-2′),
190.7 (CHO); MS (EI, 70 eV): m/z (%) = 309.4 (5.8)
[M+], 277.3 (2.2), 263.3 (74),
245.3 (50), 235.4 (100), 231.4 (24), 202.3 (65), 189.3 (19), 176.3
(2.7), 165.3 (8.8), 155.3 (7.5), 152.3 (2.7), 127.3 (9.5), 117.6
(9.1), 101.3 (19), 94.8 (7.2), 83.1 (4.7), 77.4 (10), 57.4 (2.2),
51.4 (4.0), 43.3 (2.2); Anal. Calcd for C18H15NO4:
C, 69.89; H, 4.89; N, 4.53. Found: C, 69.92; H, 4.94; N, 4.50.
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Figure 2