An Efficient and Green Oxidation of Vicinal Diols to Aldehydes Using Polymer-Supported (Diacetoxyiodo)benzene as the Oxidant

Abstract

An operationally simple and clean oxidation of a variety of vicinal diols to aldehydes using polymer-supported (diacetoxyiodo)benzene (PSDIB) has been developed in high to excellent yields. Protecting groups such as OAc, OR, OBn, OBz and iso­propylidene in the substrates were found to be stable under these reaction conditions. The regenerated PSDIB could be reused for the same reaction, affording oxidation products in high yield and purity.

polymer-supported (diacetoxyiodo)benzene - vicinal diols - oxidative cleavage - aldehydes

References and Notes

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29

Preparation of the Polymer-Supported (Diacetoxy-iodo)benzene (PSDIB).
To a mixture of CCl₄ (20 mL), H₂SO₄ (50%, 20 mL) and nitrobenzene (100 mL) was added polystyrene (5.0 g), I₂ (5.0 g, 19.7 mmol) and I₂O₅ (4.0 g, 12 mmol) at r.t. The reaction mixture was stirred under reflux for 50 h. After cooling to r.t., MeOH (500 mL) was added into the reaction mixture. The precipitates were collected by filtration and washed with MeOH (2 × 20 mL) and dried in vacuo to afford iodinated polystyrene (6.2 g). To Ac₂O (145 mL, 1.54 mol) was added dropwise 30% H₂O₂ (40 mL, 0.35 mol) and the solution was stirred at 40 °C for 4 h. Then iodinated polystyrene (6.2 g) was added and stirring was continued overnight at the same temperature. After cooling the mixture to r.t., Et₂O (100 mL) was added into the mixture. The precipitates were collected by filtration, washed with Et₂O (2 × 20 mL) and dried in vacuo to give PSDIB (6.5 g). The loading rate of functional group is 1.98 mmol/g (determined by elemental analysis).

30

Oxidation of 1a.
To a solution of 1a (3.1 g, 10 mmol) in CH₂Cl₂ (40 mL) was added PSDIB (6.06 g, 12 mmol). Then, the reaction mixture was stirred at r.t. for 7 h. Thereafter, the polymer was filtered and washed with CH₂Cl₂ (3 × 8 mL). The filtrate was poured into H₂O (45 mL), and extracted with CH₂Cl₂ (3 × 10 mL). The combined organic layer was washed with H₂O (3 × 10 mL), dried over Na₂SO₄, filtered, and the solvent was evaporated in vacuo to give crude product, which was recrystallized from PE (60-90) to afford pure 2a (2.5 g, 90%) as a white powder; mp 81.5-83 °C; [α]_D ²⁵ +28.2 (c 1.0, acetone). IR (KBr): ν = 2935, 1750, 1361, 749 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 1.26, 1.40 (s, each 3 H, i-Pr), 4.42 (d, 1 H, J = 4 Hz, C₃-H), 4.49 (d, J = 1 H, 12 Hz, C₂-H), 4.67 (t, 2 H, J = 5.6 Hz, CH₂C₆H₅), 5.07 (dd, 1 H, J = 4.8, 5.6 Hz, C₄-H), 5.27 (s, 1 H, C₁-H), 7.26-7.35 (m, 5 H, ArH), 9.65 (s, 1 H, CHO). GCMS: m/z (%) = 263 [M - CH₃]⁺, 187, 129, 113, 91 (100).