PURPOSE: To obtain a tricarbonyl intermediate for synthesizing macrolide immunosuppressant, FK-506 in a high yield with a high selectivity by reacting an aldehyde with an acetate enolate equivalent having a hydroxyl group protected, deprotecting the resultant addition product, and treating the deprotected product in the presence of oxalyl chloride and dimethyl sulfoxide.
CONSTITUTION: A 2,3-diketocarboxylate compd. of formula I is obtd. by reacting an aldehyde of formula U [wherein R is 1-40C alkyl (optionally substd. by OH, alkoxy, phenoxy, an 11-24C carbon backbone of FK-506, etc.)], with a compd. of formula III [wherein P3 is 1-10C alkyl, aryl, benzyl, etc.; X is NR1R2, OR1, or a group of formula VI (wherein R1 to R3 are each 1-4C alkyl, phenyl, or benzyl); and M is Na, K, Ca, or Al] at -100°C to 0°C in an inert org. solvent having no hydroxyl group in an inert atmosphere, removing the protective 2-hydroxyl group from the resultant compd. of formula IV, treating the deprotected compd. of formula V at a temp. of -78°C to 0°C in the presence of oxalyl chloride and dimethyl sulfoxide, and treating the resultant product with triethylamine.
DEIBUITSUDO ASUKIN
SANDAA JII MIRUZU
ROBAATO EE RIIMAA
RICHIYAADO DESUMONDO
RARUFU PII BUORANTE
DEIBUITSUDO EMU TSUSHIEN
SHINKAI ICHIRO
| JPS59157044A | 1984-09-06 | |||
| JPS62215592A | 1987-09-22 |