Subscribe to RSS
DOI: 10.1055/s-2004-825581
Reduction of 1,2-Dicarbonyl Compounds Mediated by the Combination of Phosphine and Lewis Acid
Publication History
Publication Date:
10 May 2004 (online)
![](https://www.thieme-connect.de/media/synlett/200407/lookinside/thumbnails/10.1055-s-2004-825581-1.jpg)
Abstract
The combination of Ph3P/AlBr3 effectively promoted the reduction of several 1,2-dicarbonyl compounds in the presence of water (1.0 equiv) and the corresponding α-hydroxy carbonyl compounds were obtained in good yields.
Key words
phosphorus - phosphine - Lewis acid - reduction - 1,2-dicarbonyl compounds
-
1a
Radha Rani B.Ubukata M.Osada H. Bull. Chem. Soc. Jpn. 1995, 68: 282 -
1b
Hayakawa Y.Sahara T.Shimizu M. Tetrahedron Lett. 2000, 41: 7939 -
1c
Ho T.-L.Olah GA. Synthesis 1976, 815 -
1d
Nakamura K.Kondo S.Kawai Y.Hida K.Kitano K.Ohno A. Tetrahedron: Asymmetry 1996, 7: 409 -
1e
Mashima K.Kusano K.Sato N.Matumura Y.Nozaki K.Kumobayashi H.Sayo N.Hori Y.Ishizaki T.Akutagawa S.Takaya H. J. Org. Chem. 1994, 59: 3064 -
1f
Suzuki H.Manabe H.Enokiya R.Hanazaki Y. Chem. Lett. 1986, 1339 - 2
Kagoshima H.Hashimoto Y.Oguro D.Kutsuna T.Saigo K. Tetrahedron Lett. 1998, 39: 1203 -
3a
Kagoshima H.Hashimoto Y.Saigo K. Tetrahedron Lett. 1998, 39: 8465 -
3b
Hashimoto Y.Kikuchi S. Chem. Lett. 2002, 126
References
Other phosphines, such as n-Bu3P, (o-tolyl)3P, were also examined, but Ph3P gave the best result.
5Although the generation of HBr was assumed under these conditions, it seemed that it was not involved in the reaction because the reduction did not proceed when Ph3P and HBr were used instead of Ph3P and AlBr3.
6Typical Procedure for Reduction of Benzil (Table [2] , Entry 1) : Under an argon atmosphere to a solution of AlBr3 (183.2 mg, 0.69 mmol) and benzil (103.6 mg, 0.49 mmol) in CH3CN (1 mL), which was stirred for 15 min, was added water (9 µL, 0.55 mmol). After 1 h, a solution of Ph3P (180.5 mg, 0.69 mmol) in CH3CN (2 mL) was added and stirred for 24 h. The reaction was quenched with 1 N aq HCl and the mixture was extracted with Et2O (5 × 10 mL). The combined organic layer was dried over MgSO4. This organic layer was filtered and evaporated under reduced pressure, and then the crude product was purified by preparative TLC (SiO2, CH2Cl2) to give benzoin (101.5 mg, 98% yield).