Abstract
Alcohols are converted to their corresponding 2-tetrahydrofuranyl ethers using (diacetoxyiodo)benzene
in THF. Reactions are carried out under reflux, or, more effectively, under microwave
irradiation. Yields up to 81% are reported without the use of chlorinated solvents.
Key words
hypervalent iodine -
bis -THF-ether adduct - oxidations - protecting groups - microwave
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Microwave Tetrahydrofuranylation
. PhI(OAc)2 (644 mg, 2.0 mmol), THF (2.50 mL) and decanol (0.38 mL, 2.0 mmol) were placed in
a microwave tube, with a magnetic stirrer and sealed. The tube was placed in a CEM
Discovery Microwave reactor and heated (at 100 W) to 100 °C over 5 min, then maintained
at 100 °C for 1 h. Following a 30 min cool time, the tube was removed and the contents
purified directly by flash chromatography, using 8:1 petroleum ether-Et2 O. The required fractions were concentrated under reduced pressure to afford a clear,
colorless liquid (369 mg, 81%). 1 H NMR (400 MHz, CDCl3 ): δ = 0.79 (t, 3 H), 1.10-1.30 (m, 14 H), 1.47 (pent., 2 H), 1.65-1.97 (m, 4 H),
3.28, 3.57, 3.79, 5.03. 13 C NMR (100MHz, CDCl3 ): δ = 14.4, 23.0, 23.9, 26.56, 29.62, 29.68, 29.8, 29.9, 30.1, 32.3, 32.7, 67.0,
67.6, 104.0. MS (EI, 70 eV): m/z (%) = 227 (5) [M - H+ ], 211 (7), 141 (72), 71 (100), 57 (9), 43 (28), 41 (30).
Thermal Tetrahydrofuranylation. PhI(OAc)2 (322 mg, 1.0 mmol), THF (1.25 mL) and decanol (0.19 mL, 1.0 mmol) were placed in
a microwave tube, with a magnetic stirrer and sealed. The tube was placed in an oil
bath at 85 °C, for 24 h. The THF was removed under reduced pressure, and the product
purified by flash chromatography, using 8:1 petroleum ether-Et2 O (145 mg, 61%).