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DOI: 10.1055/s-0030-1258551
N-Heterocyclic Carbene Catalyzed Vinylogous Aldol Reaction of 2-(Trimethylsilyloxy)furan and Aldehydes
Publikationsverlauf
Publikationsdatum:
03. September 2010 (online)
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Abstract
A N-Heterocyclic carbenes (NHC) catalyzed vinylogous aldol reaction between 2-(trimethylsilyloxy)furan and aldehydes has been developed, providing γ-substituted butenolides in high yields with good diastereoselectivities. Furthermore, the catalyst loading can be reduced to 1 mol%.
Key words
N-heterocyclic carbenes - vinylogous aldol reaction - butenolides - 2-(trimethylsilyloxy)furan - aldehyde
- Supporting Information for this article is available online:
- Supporting Information
- Primary data for this article are available online and can be cited using the following DOI: 10.4125/pd0004th:
- Primary Data FIDs and associated files for the ¹H and ¹³C NMR spectra for compounds 8a-m are summarized.
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References and Notes
General Procedure
for NHC-Catalyzed Vinylogous Aldol Reaction of 2-(Trimethylsilyloxy)furan
with Aldehydes
To a solution of 2 (4.0
mg, 0.012 mmol) in anhyd THF (2.0 mL) was added KOt-Bu
(1.1 mg, 0.01 mmol) under N2. After stirred for 30 min
at r.t., the solution was then cooled to 0 ˚C
and aldehyde (1.0 mmol) was added followed by 2-(trimethylsilyloxy)furan
(1.3 mmol, 200 µL). The reaction mixture was then stirred
at r.t. until full consumption of the starting aldehyde as indicated
by TLC. The solution was then cooled to 0 ˚C and
quenched with 10% aq HCl. The mixture was stirred for 30
min and neutralized by sat. aq NaHCO3 and then extracted
with EtOAc. The combined organic phase was dried over anhyd Na2SO4,
filtered, and concentrated. The ratio of anti/syn was determined by ¹H NMR
analysis of the crude products, and the configurations were assigned
by ¹H NMR comparison with literature data. The
crude products were purified through silica gel chromatography (EtOAc-PE)
to afford pure anti products or a mixture
of anti/syn isomers.
Data for 8g
Yield 83%;
white solid; R
f
= 0.14
(PE-EtOAc, 4:1); mp 134.5-135.5 ˚C. ¹H
NMR (400 MHz, CDCl3): δ = 7.61 (dd, J = 7.6, 1.2
Hz, 1 H), 7.20-7.45 (m, 4 H), 6.20 (dd, J = 5.6, 2.0
Hz, 1 H), 5.62 (t, J = 4.0
Hz, 1 H), 5.36-5.44 (m, 1 H), 3.36 (d, J = 4.4
Hz, 1 H). ¹³C NMR (100 MHz, CDCl3): δ = 172.3,
151.2, 134.5, 130.8, 128.6, 126.9, 126.4, 122.5, 83.6, 68.4. IR
(KBr): ν = 3390, 1726, 1465, 1437, 1342, 1188, 1108,
1025, 918, 819, 744, 609 cm-¹. ESI-HRMS: m/z calcd for C11H9ClO3Na:
247.0132; found: 247.0156.