Enolboration of conjugated ketones and synthesis of beta-amino alcohols and boronated alpha-amino acids

Zaidlewicz, M.; Sokól, W.; Wolan, A.; Cytarska, J.; Tafelska-Kaczmarek, A.; Dzielendziak, A.; Prewysz-Kwinto, A.

doi:10.1351/pac200375091349

Pure Appl. Chem., 2003, Vol. 75, No. 9, pp. 1349-1355

http://dx.doi.org/10.1351/pac200375091349

Enolboration of conjugated ketones and synthesis of beta-amino alcohols and boronated alpha-amino acids

M. Zaidlewicz, W. Sokól, A. Wolan, J. Cytarska, A. Tafelska-Kaczmarek, A. Dzielendziak and A. Prewysz-Kwinto

Department of Chemistry, Nicolaus Copernicus University, 87-100 Torun, Poland

Abstract: Enolization–aldolization of conjugated ketones, enantioselective synthesis of benzofuryl beta-amino alcohols, and synthesis of p-dihydroxyborylphenylalanine (BPA) and its analogs are described. Aldolization of benzaldehyde with lithium dienolates derived from unhindered conjugated cyclohexenones favored anti- selectivity, whereas syn selectivity was favored for hindered cyclohexenones. Anti-aldols were preferentially formed from dienolborinates derived from conjugated cyklohexenones, however,competing aldolization at the 2-position was observed for hindered ketones. Benzofuryl beta-amino alcohols were prepared using as a key step the enantioselective reduction of the corresponding alpha-bromoacetylbenzofurans with (–)-B- -chlorodiisopinocampheylborane. Ionic liquids were used as solvents for the synthesis of BPA by the Suzuki cross-coupling reaction. The reaction time is short, and a solution of the catalyst in the ionic liquid can be recycled.