RSS-Feed abonnieren
DOI: 10.1055/s-2003-39307
Concerning Tishchenko-Like Side Products in Oxidation of Hydroxymethyl to Formyl Groups
Publikationsverlauf
Publikationsdatum:
20. Mai 2003 (online)
![](https://www.thieme-connect.de/media/synlett/200307/lookinside/thumbnails/10.1055-s-2003-39307-1.jpg)
Abstract
Oxidation of a hydroxymethyl group to an aldehyde sometimes gives a dimeric ester reminiscent of a Tishchenko aldehyde-ester disproportionation. This process has been observed only with Cr(VI)/pyridine based reagents, and can be avoided most notably by using Dess-Martin and Swern (DMSO/COCl2) reagents.
Key words
Tishchenko - Cr(VI)/pyridine based reagents - oxidation
- 1
Ermolenko L.Sasaki NA.Potier P. Synlett 2001, 1565 - 2
Yunker MB.Fraser-Reid B. J. Chem. Soc., Chem. Commun. 1975, 61 - 4
Tishchenko J. Russ. Phys. Chem. Soc. 1906, 38: 355 -
5a
Saegusa T.Ueshima T. J. Org. Chem. 1968, 33: 3310 -
5b
Buehler CA.Pearson DE. Survey of Organic Synthesis Vol. 2: John Wiley and Sons; New York: 1977. p.754 -
5c
March J. Advanced Organic Chemistry 4th ed: John Wiley and Sons; New York: 1992. p.235 - 6
Ito J.Horino H.Koshiro Y.Yamamoto A. Bull. Chem. Soc. Jpn. 1982, 55: 504 - 7 For a review see:
Geissman TA. Org. React. 1944, 2: 94 - 8
Stapp PR. J. Org. Chem. 1973, 38: 1433 - 9
Yamashita M.Watanbe Y.Mitsudo T.Takegami Y. Bull. Chem. Soc. Jpn. 1976, 49: 3597 - 10
Corey EJ.Schmidt G. Tetrahedron Lett. 1979, 5: 399 - 11
Piancatelli G.Scettri A.D’Aure M. Synthesis 1982, 245 - 12
Mancuso AJ.Huang S.-L.Swern D. J. Org. Chem. 1978, 47: 2480 - 13
Frigerio M.Santagostino M.Sputore S. J. Org. Chem. 1999, 64: 4537
References
Synthesis of Ester 7b from 5b with PCC: To a stirred mixture of PCC (129.4 g), sodium acetate (49.2 g), molecular sieves (120 g) in CH2Cl2 (600 mL) at ambient temperature was added a solution of alcohol 5b (38.8 g) in 100 mL of CH2Cl2. After 5 h, the mixture was filtered through a pad of Celite and washed with CH2Cl2. The combined filtrate and washings was passed through a pad of celite and a pad of silica gel. Removal of the solvent by rotatory evaporation gave 50 g crude product mixture with a 6b:7b ratio of 1:19 estimated by 1H NMR. Pure 7b (5.2 g) was obtained from 10 g of the crude product mixture by flash chromatography eluted with hexane-EtOAc (7:3). 1H NMR (CDCl3): δ = 7.2-7.3 (m, 10 H), 5.3-5.5 (2 s, 2 H), 3.6-4.6 (m, 10 H), 1.2-2.2 (m, 6 H) ppm. 13C NMR (CDCl3): δ = 170.5, 139.0, 138.5, 129.5 (2 C), 129.38 (2 C), 128.74 (2 C), 126.85 (2 C), 126.68 (2 C), 101.78, 101.69, 75.95, 75.16, 67.49, 67.13, 67.03, 28.75, 28.00 ppm. GC-MS: 384 (M).
14Synthesis of Aldehyde 6b from 6b with Dess-Martin Periodinane: To a stirred mixture of alcohol 5b (35 g), pyridine (87 mL) and anhyd DCM (500 mL) was added a cooled solution of DMP (15 wt% in CH2Cl2, 1000 mL) in 20 min. The mixture was stirred at ambient temperature for 22 h. The reaction mixture was concentrated to 500 mL under reduced pressure, then diluted with 2 L of EtOAc followed by 100 mL of aq 2 M NaOH. After stirred for 1 h, the white precipitate was removed by filtration through a pad of Celite and washed with EtOAc. The combined filtrate and washings was washed with 100 mL of sat. NaHCO3 and 100 mL of brine, dried over Na2SO4 (200 g) overnight, filtered, concentrated to dryness under reduced pressure. The residue was purified on 350 g of silica gel eluted with hexane-EtOAc 1/0 to 7/3 to give 24.8 g of aldehyde 6b in 72% yield. 1H NMR (CDCl3): δ = 9.62 (s, 1 H), 7.2-7.6 (m, 5 H), 5.50 (s, 1 H), 4.1-4.3 (m, 2 H), 3.75-3.85 (m, 1 H), 1.6-2.0 (m, 2 H) ppm. 13C NMR (CDCl3): δ = 200.68, 138.52, 129.69, 128.86 (2 C), 126.77 (2 C), 101.63, 80.88, 66.94, 26.40. GC-MS: 192 (M).