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DOI: 10.1055/s-0029-1218376
The Highly Efficient 1,4-Addition of TMSCN to Aromatic Enones Catalyzed by CsF with Water as the Additive
Publikationsverlauf
Publikationsdatum:
18. November 2009 (online)
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Abstract
An efficient 1,4-addition of TMSCN to aromatic enones has been achieved in excellent yields (91-99%) by CsF (1 mol%) as the catalyst and H2O (4 equiv) as the additive in refluxing dioxane within 2-7 hours.
Key words
1,4-addition reaction - enones - nitriles - regioselectivity - CsF
- Supporting Information for this article is available online:
- Supporting Information
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References and Notes
See Supporting Information.
21
Preparation of
2a
The solution of CsF (0.5 mg, 0.003 mmol,
1 mol%) and enone (1a, 62.5 mg,
0.3 mmol) in dioxane (1 mL) is added TMSCN (84 µL, 0.66
mmol, 2.2 equiv) and H2O (22 µL, 1.2 mmol, 4
equiv) subsequently in a dry Schlenk tube equipped with cold finger
under argon. The reaction mixture is stirred at reflux temperature
until the reaction is completed (monitored by TLC). 1 M HCl (0.3
mL) is added to quench the reaction with additional 20 min stirring
at r.t. The resulting mixture is extracted with EtOAc (5 mL) (Caution! HCN
generated in the reaction mixture is highly toxic. Those operations
should be conducted in a well-ventilated hood). The extract is washed
with H2O, brine, dried over anhyd Na2SO4,
and concentrated. The crude product is purified by flash chromatography
on silica gel (PE-EtOAc, 20:1) to afford 2a as
white solid in 99% yield.
Nitrile 2a:
mp 120-122 ˚C (lit.: 122-125 ˚C).¹¹ ¹H
NMR (400 MHz, CDCl3): δ = 3.52 (dd, J = 6.0, 18.0
Hz, 1 H, NCCHCH
A
HBCO),
3.74 (dd, J = 8.0,
18.0 Hz, 1 H, NCCHCHA
H
B
CO), 4.57 (dd, J = 6.0,
8.0 Hz, 1 H, NCCHCHAHBCO),
7.34-7.49 (m, 7 H, ArH), 7.58-7.62 (m, 1 H, ArH),
7.92-7.94 (m, 2 H, ArH) ppm. ¹³C
NMR (100 MHz, CDCl3): δ = 31.9, 44.5,
120.6, 127.5, 128.1, 128.4, 128.8, 129.3, 133.9, 135.3, 135.8, 194.6
ppm. IR (KBr): ν = 1681, 2236 cm-¹.