[37675-33-5]  · C3H5BrO  · 3-Bromo-2-propen-1-ol  · (MW 136.98)

(used in palladium-catalyzed cross-coupling reactions with alkynes)

Physical Data: bp 94-97 °C/55 mmHg. cis isomer: bp 81 °C/25 mmHg; d25 1.6623. trans isomer: bp 87 °C/25 mmHg; d25 1.6567.

Analysis of Reagent Purity: satisfactory microanalytical data reported.1

Preparative Methods: by alkaline hydrolysis of 1,3-dibromopropene,1,2 by hydrobromination of methyl propiolate followed by reduction,3 or by sequential hydrostannylation and bromination of propyn-3-ol.4

3-Bromo-2-propen-1-ol has been widely used in palladium-catalyzed cross-coupling reactions of hydroxylated alkynes. Synthetic routes to leukotriene B4,5 leukotriene E4 metabolites,4 lipoxin A1,6 coriolic acid, and dimorphecolic acid7 have utilized such reactions as pivotal steps (eqs 1-4, respectively). Intermediates for the preparation of other arachadonic acid metabolites have also been prepared by this method (eq 5).8

Trienals derived from linolenic acid may be prepared using the process (eq 6).9

Oxidation of bromopropenal gives the highly unstable 3-bromopropenal that may be converted in situ to the corresponding dimethyl acetal (eq 7), which has been examined as a substrate for Heck reactions with alkenes.4

1. Hatch, L. F.; Harwell, K. E. JACS 1953, 75, 6002.
2. Patel, B. A.; Kim, J-I. I.; Bender, D. A.; Kao, L-C.; Heck, R. F. JOC 1981, 46, 1061.
3. MacInnes, I.; Schorstein, D. E.; Suckling, C. J.; Wrigglesworth, R. JCS(P1) 1981, 1103.
4. Delorme, D.; Girard, Y.; Rokach, J. JOC 1989, 54, 3635.
5. Nicolaou, K. C.; Zipkin, R. E.; Dolle, R. E.; Harris, B. D. JACS 1984, 106, 3548.
6. Nicolaou, K. C.; Marron, B. E.; Veale, C. A.; Webber, S. E.; Serhan, C. N. JOC 1989, 54, 5527.
7. Rao, A. V. R.; Reddy, E. R.; Sharma, G. V. M.; Yadagiri, P.; Yadav, J. S. TL 1985, 26, 465; T 1986, 42, 4523.
8. Kaye, A. D.; Pattenden, G. TL 1986, 27, 2033.
9. Bohlmann, F.; Rotard, W. LA 1982, 1216.

Joseph Sweeney

University of Bristol, UK

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