Abstract
A rapid oxidation of primary and secondary alcohols using catalytic amounts of TEMPO
and Yb(OTf)3 in combination with a stoichiometric amount of iodosylbenzene (PhIO) is described.
This procedure operates at room temperature or above to afford carbonyl compounds
in excellent yields without over-oxidation to carboxylic acids. Oxidation of primary
alcohols in the presence of secondary alcohols proceeded with good selectivity.
Key words
alcohols - iodosylbenzene - oxidation - TEMPO - ytterbium trifluoromethanesulfonate
References and Notes
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Oxidation of Monoalcohols (Table 2) and Diols (Table 3, entries 1, 4, and 5); General
Procedure. To a stirred solution of alcohol (1 mmol) in CH2 Cl2 (4 mL) were added TEMPO (8 mg, 5 mol%) and PhIO (286 mg, 1.3 equiv). The suspension
was cooled to 0 °C and Yb(OTf)3 (12.5 mg, 2 mol%) was added. The reaction mixture was stirred at 0 °C or r.t. depending
on the substrate until the alcohol was no longer detectable by TLC (the reaction mixture
became almost limpid). The yellow slightly cloudy solution was poured onto a column
of silica gel (10 g) and eluted with Et2 O-PE. The purity of each aldehyde or ketone was checked by NMR spectroscopy.
<A NAME="RD09006SS-18">18 </A>
In the presence of 1.3 equivalent of PhIO, cis -1,2-cyclo-hexanedimethanol gave the γ-lactone (55% yield) and lactols (9%); 30% of
the diol was recovered (as compared to Table 3, entry 2).
<A NAME="RD09006SS-19">19 </A>
Oxidative Lactonization of Diols (Table 3, entry 2); Typical Procedure. To a solution of cis -1,2-cyclo-hexanedimethanol (0.15 g, 1.04 mmol) in CH2 Cl2 (5 mL) were added PhIO (0.594 g, 2.6 equiv) and TEMPO (16 mg, 0.1 equiv). The suspension
was cooled to 0 °C and Yb(OTf)3 ·xH2 O (26 mg, 0.04 equiv) was added. The reaction was stirred at r.t. for 1 h and poured
onto a column of silica gel. Elution with PE-Et2 O (1:1) gave cis -perhydro-phthalide (0.14 g, 96%) as an oil. 13 C and 1 H NMR data were identical with those described in the literature.
