Development of a rhodium carbenoid-initiated claisen rearrangement for the enantioselective synthesis of α-hydroxy carbonyl compounds [1]

Journal of the American Chemical Society

Volumn 121, Issue 8, 1999, Pages 1748-1749

  Wood, John L ^a   Moniz, George A ^a   Pflum, Derek A ^a   Stoltz, Brian M ^a   Holubec, Alexandra A ^a   Dietrich, Hans Jürgen ^a  

^a YALE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL; CARBONYL DERIVATIVE; ESTER; RHODIUM;

CATALYSIS; CATALYST; CHROMATOGRAPHY; DIASTEREOISOMER; LETTER; STEREOCHEMISTRY; SYNTHESIS;

EID: 0033518872     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja983294l     Document Type: Letter

References (14)

1. For a recent review, see: Miller, D. J.; Moody, C. J. Tetrahedron 1995, 51, 10811.
2. For a recent and elegant stereoselective preparation of α-hydroxy carbonyls, see: Evans, D. A.; Kozlowski, M. C.; Burgey, C. S.; MacMillan, D. W. C. J. Am. Chem. Soc. 1997, 119, 7893.
3. (a) Koreeda, M.; Luengo, J. I. J. Am. Chem. Soc. 1985, 107, 5572.
4. (b) Examples of both [2,3] and [3,3] rearrangement of α-allyloxy ketones have been reported, see: Ziegler, F. E. Chem. Rev. 1988, 88, 1423 and references therein.
5. 4 (30 mg, 0.068 mmol), and heated to reflux. After 20 min at reflux the reaction is cooled, and the solvent removed in vacuo. Chromatographic purification (20% EtOAc/Hex) furnishes 3.20 g of 5 (77% yield, 95% ee).
6. Evans, D. A.; Golub, A. M. J. Am. Chem. Soc. 1975, 97, 4765.
7. 13C (125 MHz) spectra, as well as with appropriate parent ion identification by high-resolution mass spectrometry. Details regarding the assignment of relative and absolute stereochemistry are included as Supporting Information.
8. For the preparation of 6, see: Davies, H. M. L.; Houser, J. H.; Thornley, C. J. Org. Chem. 1995, 60, 7529.
9. The reported yield for 7 includes three silylated products, see Supporting Information for details.
10. 1H NMR. (Figure Presented)
11. Experiments in this series were performed with racemic alcohol as substrate. Thus, where defined, the structures illustrate only relative stereochemistry.
12. Although the transient species 9 can be envisioned with or without rhodium, the known influence of asymmetric rhodium catalysts on other sigmatropic rearrangements suggests its inclusion, see: Pierson, N.; Fernádez-Garciá; C.; McKervey, M. A. Tetrahedron Lett. 1997, 38, 4705.
13. Acid-promoted tautomerization of 10 would account for observations of 12 by TLC.
14. The inclusion and recovery of 14 in this experiment provides positive proof against its intermediacy en route to 13. The structure of 13 was confirmed via chemical correlation, see Supporting Information.