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DOI: 10.1055/s-0030-1259932
Catalytic Enantioselective Friedel-Crafts Alkylation of Indoles with β,γ-Unsaturated α-Keto Phosphonates in the Presence of Chiral Palladium Complexes
Publikationsverlauf
Publikationsdatum:
30. März 2011 (online)

Abstract
The catalytic enantioselective Friedel-Crafts alkylation reaction promoted by chiral palladium complexes is described. The treatment of indoles with β,γ-unsaturated α-keto phosphonates under the mild reaction conditions afforded the corresponding Friedel-Crafts alkylation adducts with excellent enantioselectivities (up to 99% ee).
Key words
Friedel-Crafts reaction - asymmetric catalysis - chiral palladium catalysts - indoles - β,γ-unsaturated α-keto phosphonates
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References and Notes
Typical Procedure
To
a stirred solution of (E)-diethyl 1-oxobut-2-enylphos-phonate
(2a, 20.6 mg, 0.1 mmol), Pd catalyst 1c (5.4 mg, 0.005 mmol) in CH2Cl2 (1
mL) was added indole (3a, 14.0 mg, 0.12
mmol) at r.t. The reaction mixture was stirred for 2 h at r.t. Then
MeOH (0.15 mL), followed by DBU (0.03 mL), was added directly to
the reaction mixture. The reaction was allowed to stir for 2 h at
r.t. The reaction was diluted with EtOAc (10 mL), then washed with
sat. NH4Cl. The organic layer was dried over anhyd MgSO4,
filtered, concentrated, and purified by flash column chromatography (EtOAc-hexane,
1:5) to afford (S)-methyl 3-(1H-indol-3-yl)butanoate (4a,
70%, 15.2 mg). [α]D
²8 7.3
(c 0.7, CHCl3, 93% ee). ¹H
NMR (200 MHz, CDCl3): δ = 7.99
(br s, 1 H), 7.63 (d, J = 7.8
Hz, 1 H), 7.28 (d, J = 7.6
Hz, 1 H), 7.23-7.05 (m, 2 H), 6.90 (d, J = 2.5
Hz, 1 H), 3.65-3.47 (m, 1 H), 3.62 (s, 3 H), 2.82 (dd, J = 14.8,
6.0 Hz, 1 H), 2.56 (dd, J = 14.7, 8.7
Hz, 1 H), 1.39 (d, J = 6.9
Hz, 3 H). ¹³C NMR (50 MHz, CDCl3): δ = 173.0,
136.1, 125.9, 121.5, 120.2, 119.7, 118.8, 118.7, 110.9, 51.1, 41.9,
27.6, 20.6. ESI-MS: m/z = 217.9 [M + H]+,
117.0, 120.9, 123.0 147.0, 176.9. HPLC (hexane-i-PrOH = 90:10, 220 nm, 0.8
mL/min) Chiralcel OD-H column, t
R = 9.0
min(minor), t
R = 13.8
(major).
The two-site-binding interaction between substrate and palladium catalyst is crucial to guarantee reactivity as well as stereocontrol. In fact, when the monodentate ethyl (E)-but-2-enoate was reacted with indole under the same reaction conditions, no reaction occurred.