Practical synthesis of an L-fructose-derived ketone catalyst for asymmetric epoxidation of olefins

Journal of Organic Chemistry

Volumn 71, Issue 14, 2006, Pages 5377-5379

  Zhao, Mei Xin ^a   Shi, Yian ^a  

^a Department of Ecosystem Science and Sustainability   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EPOXIDATION; L-FRUCTOSE-DERIVED KETONE; L-SORBOSE; TRI SUBSTITUTED OLEFINS;

CATALYSTS; FRUCTOSE; OLEFINS; OXIDATION; REACTION KINETICS; SYNTHESIS (CHEMICAL);

KETONES;

ALCOHOL; ALKENE; FRUCTOSE; KETONE; MESYLIC ACID; SORBOSE;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CATALYST; CHEMICAL REACTION; CHEMICAL STRUCTURE; EPOXIDATION; PROTON NUCLEAR MAGNETIC RESONANCE; SYNTHESIS;

ALKENES; CATALYSIS; EPOXY COMPOUNDS; FRUCTOSE; KETONES; MOLECULAR CONFORMATION; SORBOSE; STEREOISOMERISM;

EID: 33745700292     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo060335k     Document Type: Article

References (22)

1. For reviews on chiral ketone-catalyzed asymmetric epoxidation, see: (a) Denmark, S. E.; Wu, Z. Synlett 1999, 847.
2. (b) Frohn, M.; Shi, Y. Synthesis 2000, 1979.
3. (c) Shi, Y. Acc. Chem. Res. 2004, 37, 488.
4. (d) Yang, D. Acc. Chem. Res. 2004, 37, 497.
5. (a) Tu, Y.; Wang, Z.-X.; Shi, Y. J. Am. Chem. Soc. 1996, 118, 9806.
6. (b) Wang, Z.-X.; Tu, Y.; Frohn, M.; Zhang, J.-R.; Shi, Y. J. Am. Chem. Soc. 1997, 119, 11224.
7. (c) Shu, L.; Shi, Y. Tetrahedron 2001, 57, 5213.
8. Tu, Y.; Frohn, M.; Wang, Z.-X.; Shi, Y. Org. Synth. 2003, 80, 1.
9. Chen, C.-C.; Whistler, R. L. Carbohydr. Res. 1988, 175, 265.
10. For a stepwise synthesis of L-fructose from L-sorbose, see: Bach, T.; Hofer, F. J. Org. Chem. 2001, 66, 3427.
11. For examples using ketone ent-1, see: (a) Morimoto, Y.; Iwai, T.; Kinoshita, Tetrahedron Lett. 2001, 42, 6307.
12. (b) Morimoto, Y.; Takaishi, M.; Iwai, T.; Kinoshita, T.; Jacobs, H. Tetrahedron Lett. 2002, 43, 5849.
13. (c) Altmann, K.-H.; Bold, G.; Caravatti, G.; Denni, D.; Flörsheimer, A.; Schmidt, A.; Rihs, G.; Wartmann, M. Helv. Chim. Acta 2002, 85, 4086.
14. (d) Zhang, Q.; Lu, H.; Richard, C.; Curran, D. P. J. Am. Chem. Soc. 2004, /26, 36.
15. 4 per gram of substrate) was found to work well. A prolonged reaction time could also lead to the decomposition of the compound.
16. Although a higher concentration of base can accelerate the reaction, the reaction mixture becomes complex. Considering the reaction efficiency and stability of the product, using 9 M NaOH and refluxing for 8 h worked well.
17. The reaction should be carefully monitored by TLC and quenched as soon as the reaction is finished. Heating the reaction mixture for a long time causes problems, possibly polymerization of the L-fructose.
18. Large quantities of L-sorbose were purchased from MP Biomedicals, LLC (Aurora, OH).
19. The GC retention time of the main peak is 3.32 min. Conditions: column, VA-5MS, Varian chromatography systems (VA-122553-20); oven, from 150 to 250°C (20°C/min); carrier, helium, head pressure 25 psi; detection: FID 250°C.
20. f/values of compounds 4, 5, and 6 are 0.57, 0.70, and 0.30, respectively, using EtOAc as a solvent.
21. The obtained L-fructose was a sticky syrup. Freezing the syrup with dry ice led to a solid which was easier to manipulate.
22. Alcohol 7 is the kinetic product of the reaction. Controlling the reaction time is important to minimize its isomerization to the thermodynamic product. The GC retention time of the main peak is 4.42 min. Conditions: column, VA-5MS, Varian chromatography systems (VA-122553-20); oven, 170°C; carrier, helium, head pressure 25 psi; detection, FID 250°C.