[10465-81-3]  · C12H20N4O2  · 1,1-(Azodicarbonyl)dipiperidine  · (MW 252.32)

(selectively oxidizes a variety of alcohols to the corresponding aldehydes or ketones under basic conditions1)

Physical Data: mp 134-135 °C.

Solubility: insol petroleum ether; slightly sol methanol; sol ethanol, ether, THF.

Form Supplied in: golden-yellow crystals.

Analysis of Reagent Purity: 1H NMR (CCl4) d 1.47-1.88 (12H, br), 3.15-3.77 (8H, br); IR (KBr) 1705 cm-1.

Purification: recrystallized from hexane-benzene (10:1).

Handling, Storage, and Precautions: irritant; stable to storage at room temperature.

Oxidation of Alcohols.

A wide variety of primary and secondary alcohols, after being converted into their bromomagnesium salts by treatment with a slight excess amount (1.2 equiv) of n-propylmagnesium bromide or t-Butoxymagnesium Bromide, are oxidized with 1.2 equiv of 1,1-(azodicarbonyl)-dipiperidine in THF at room temperature to afford the corresponding aldehydes or ketones in high yield (eq 1).1

The use of t-butoxymagnesium bromide is recommended for the oxidation of the substrates having functional groups which react with Grignard reagents. The oxidation of testosterone proceeds smoothly to give 4-androstene-3,17-dione in high yield by the use of t-butoxymagnesium bromide (eq 2).1

This method has been employed to oxidize a wide range of alcohols incorporating functional groups such as alkenes, epoxides, amines, sulfides (eq 3),2 allylstannanes (eqs 4 and 5),3,4 and allenylstannanes (eq 6).5 Acylstannanes can also be prepared by the oxidation of the lithium salt of 1-stannyl alcohols (eq 7).6

1. Narasaka, K.; Morikawa, A.; Saigo, K.; Mukaiyama, T. BCJ 1977, 50, 2773.
2. Meyers, A. I.; Comins, D. L.; Roland, D. M.; Henning, R.; Shimizu, K. JACS 1979, 101, 7104.
3. Marshall, J. A.; Gung, B. W. Isr. J. Chem. 1991, 31, 199.
4. Denmark, S. E.; Weber, E. J. JACS 1984, 106, 7970.
5. Marshall, J. A.; Wang, X.-j. JOC 1992, 57, 3387.
6. Marshall, J. A.; Gung, W. Y. T 1989, 45, 1043.

K. Narasaka & H. Kusama

The University of Tokyo, Japan

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