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DOI: 10.1055/s-0030-1258032
Photodecarboxylative Additions of α-Thioalkyl-Substituted Carboxylates to Alkyl Phenylglyoxylates
Publikationsverlauf
Publikationsdatum:
12. August 2010 (online)
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Abstract
Irradiations of alkyl phenylglyoxylates with sulfur-containing carboxylates yielded the corresponding photodecarboxylative addition products in moderate to good yields of 26-58%. Reductive photodimerization competed with decarboxylative addition in all cases. The reaction protocol was successfully transferred to a microreactor. With potassium 2-(methylsulfanyl)propionate, photoadditions gave diastereomeric mixtures with low selectivity for the like-isomer.
Key words
photodecarboxylation - phenylglyoxolates - photochemistry - photoinduced electron transfer, microreactor
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References and Notes
General Procedure
for Irradiation
The alkyl phenylglyoxylate (1.5 mmol)
was dissolved in MeCN (50 mL). A solution of the potassium carboxylate (4.5
mmol) in H2O (50 mL) was added, and the mixture was irradiated
(Rayonet Photochemical Reactor RPR-200; λ = 350 ± 30
nm) at 15-20 ˚C in a Pyrex tube (λ ³ 300
nm) while purging with a slow stream of nitrogen. The progress of
the reaction was monitored by TLC analysis or by passing the departing
gas stream through a sat. Ba(OH)2 solution until precipitation
of BaCO3 had ceased. Most of the MeCN was evaporated,
and the remaining solution was extracted with EtOAc (4 × 25
mL). The combined organic layers were washed with 5% NaHCO3 (1 × 25
mL) and brine (1 × 25 mL), dried over MgSO4,
and evaporated. The products were purified by flash column
chromatography (eluent:
n-hexane-EtOAc = 5:1).
Selected Physical and Spectral Data for the
Product Methyl-2-(1,3-dithian-2-yl)-2-hydroxy-2-phenylacetate (4e)
Yellowish
solid, mp 104-106 ˚C. R
f
= 0.39 (SiO2, n-hexane-EtOAc = 5:1). ¹H
NMR (400 MHz, acetone-d
6): δ = 1.84
(m, 2 H, CH2), 2.40-2.46 (m, 1 H, SCH2),
2.56-2.62 (m, 1 H, SCH2), 3.02-3.09
(m, 1 H, SCH2), 3.19-3.26 (m, 1 H, SCH2),
3.61 (s, 3 H, OCH3), 4.48 (s, 1 H, CH), 5.14 (s, 1 H, OH),
7.14-7.24 (br m, 3 H, Harom), 7.56 (dd, ³
J = 8.4 Hz, 4
J = 1.6 Hz,
2 H, Harom) ppm. ¹³C NMR
(100 MHz, CDCl3): δ = 25.1 (t, 1 C,
CH2), 28.0 (t, 1 C, SCH2), 28.3 (t, 1 C, SCH2),
50.4 (d, 1 C, CH), 53.9 (q, 1 C, OCH3), 85.1 (s, 1 C, COH),
126.0 (d, 2 C, CHarom), 128.3 (d, 1 C, CHarom),
128.4 (d, 2 C, CHarom), 139.1 (s, 1 C, Cqarom),
173.8 (s, 1 C, C=O) ppm. IR (KBr): ν = 3490,
2953, 2925, 2892, 1725, 1239, 733, 692 cm-¹.
MS (EI, 70 eV): m/z (%) = 284
(<1) [M+], 119 (100) [M+ - H2O],
105 (12), 91 (4), 77 (14), 45 (5).
The dwell-reactor is made out of Foturan glass (λ ³ 300 nm) and has a total path length of 1.15 m (20 turns) on a 118 mm × 73 mm aperture. The reactor consisted of a(bottom) serpentine reaction channel 0.5 × 2 mm (D × W), with a second(top), heat-exchanging channel through which water is passed in order to control the reactor temperature. The degassed reaction mixture (20 mL)8 was pumped through the reaction channel via a syringe pump and collected in a test tube.
16Irradiation of 2 in benzene and in the presence of 5 equiv of Me2S gave the corresponding addition product 5a in a yield of 35%. Selectivity (7 vs. 5a) was determined as 60:40. Similar results were obtained with 1,3-dithiolane.³a