Scalable methodology for the catalytic, asymmetric α-bromination of acid chlorides

Journal of Organic Chemistry

Volumn 71, Issue 23, 2006, Pages 8946-8949

  Dogo Isonagie, Cajetan ^a   Bekele, Tefsit ^a   France, Stefan ^a   Wolfer, Jamison ^a   Weatherwax, Anthony ^a   Taggi, Andrew E ^a,b   Lectka, Thomas ^a  

^a JOHNS HOPKINS UNIVERSITY   (United States)

^b DUPONT COMPANY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBOXYLIC ACIDS; CATALYSIS; CATALYST SELECTIVITY; ESTERS; REACTION KINETICS; STEREOCHEMISTRY;

ALPHA-BROMOESTERS; CHEMICAL YIELDS; ENANTIOSELECTIVITY; PROLINE CINCHONA ALKALOID;

ALKYLATION;

ACID CHLORIDE; ALKALOID DERIVATIVE; CHLORIDE; CINCHONA ALKALOID; PROLINE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; BROMINATION; CARBON NUCLEAR MAGNETIC RESONANCE; CATALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; METHODOLOGY; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION OPTIMIZATION; STOICHIOMETRY;

BROMINE; CATALYSIS; ESTERS; HYDROCARBONS, CHLORINATED; MOLECULAR STRUCTURE; STEREOISOMERISM;

EID: 33750883919     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo061522l     Document Type: Article

References (20)

1. Hafez, A. M.; Taggi, A. E.; Wack, H.; Esterbrook, J.; Lectka, T. Org. Lett. 2001, 3, 2049-2051.
2. For example, see: (a) Qian, X.; Zheng, B.; Burke, B.; Saindane, M. T.; Kronenthal, D. R. J. Org. Ghent. 2002, 67, 3595-3600.
3. (b) Dutton, F. E.; Lee, B. H.; Johnson, S. S.; Coscarelli, E. M.; Lee, P. H. J. Med. Chem. 2003, 46, 2057-2073.
4. Taggi, A. E.; Hafez, A. M.; Wack, H.; Young, B.; Ferraris, D.; Lectka, T. J. Am. Chem. Soc. 2002, 124, 6626-6636. Also, see ref 18.
5. Kacprzak, K.; Gawronski, J. Synthesis 2001, 7, 961-998.
6. Taggi, A. E.; Hafez, A. M.; Dudding, T.; Lectka, T. Tetrahedron 2002, 58, 8351-8356.
7. France, S.; Guerin, D. J.; Miller, S. J.; Lectka, T. Chem. Rev. 2003, 103, 2985-3012.
8. Standard reaction conditions with phenoxypropionyl chloride: 10 mol % cat., NaH as base, 10 mol % 15-crown-5, in THF at -78 "C. Also, see the Supporting Information.
9. France, S.; Wack, H.; Taggi, A. E.; Hafez, A. M.; Wagerle, T. R.; Shah, M. H.; Dusich, C. L.; Lectka, T. J. Am. Chem. Soc. 2004, 126, 4245-4255.
10. Polymer-bound BEMP resin (2-tert-butylimino-2-diethylamino-1,3-dimethyl- perhydro-1,3,2-diazaphosphorine) is commercially available from Aldrich Chemical Co.
11. For a detailed description of a ketene-forming reaction employing BEMP as base, see: Wack, H.; Taggi, A. E.; Hafez, A. M.; Drury, W. J.; Lectka, T. J. Am. Chem. Soc. 2001, 123, 1531-1532.
12. Shah, M. H.; France, S.; Lectka, T. Synlett 2003, 12, 1937-1939.
13. Taggi, A. E.; Wack, H.; Hafez, A. M.; France, S.; Lectka, T. Org. Lett. 2002, 4, 627-629.
14. The "double barrel" flask is made up of two reaction flasks separated by a glass frit. See ref 5 for a full description of the flask (commercially available from Chemglass).
15. Wack, H.; Taggi, A. E.; Hafez, A. M.; Drury, W. J.; Lectka, T. J. Am. Chem. Soc. 2001, 123, 1531-1532.
16. Preliminary data support tight ion pairing. Further mechanistic studies are being conducted and will be published in due course.
17. Calo, V.; Ciminale, F.; Lopez, L.; Todesco, P. J. Chem. Soc. C 1971, 21, 3652-3653. The brominating reagent 4a is commercially available from Aldrich. Also, see ref 5 for a synthetic procedure.
18. (a) Fries, K.; Engel. Liebigs Ann. Chem. 1924, 439, 237-245.
19. (b) Janney, N. W. Liebigs Ann. Chem. 1913, 398, 365-372.
20. The synthesis of quinone 4d is similar to that reported for the related trichloroquinone, see: France, S.; Wack, H.; Taggi, A. E.; Hafez, A. M.; Wagerle, T. R.; Shah, M. H.; Dusich, C. L.; Lectka, T. J. Am. Chem. Soc. 2004, 126, 4245-4255.