Proline cci-779 (proline-rapamycin 42-ester with 2,2-bis...

C - Chemistry – Metallurgy – 07 – D

Patent

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Details

C07D 498/18 (2006.01) C07F 7/18 (2006.01)

Patent

CA 2564811

Disclosed are proline-rapamycin 42-ester with 2,2-bis(hydroxymethyl)propionic acid (proline-CCI-779) as well as a method for the regiospecific preparation of a rapamycin 42-ester or proline-rapamycin 42-ester with 2,2- bis(hydroxymethyl)propionic acid (CCI-779 and proline-CCI-779) comprising the steps of: (a) reacting rapamycin or proline-rapamycin with an activated ester derivative of 2,2-bis(hydroxymethyl)propionic acid having the structure (A) wherein R1 and R2 are hydrogen, or taken together to form a ketal with the structure (B) wherein R3 and R4 are each, independently, hydrogen, C1-6 alkyl, either linear or branched, or taken together form C5-7 cycloalkyl or taken together form cyclic boronate with the structure (C), wherein R5 is selected from methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl and phenyl; in a suitable organic solvent in the presence of an effective amount of microbial lipase; and (b) deprotecting the intermediate resulting from step (a) to provide CCI-779 or proline-CCI-779.

L'invention concerne un ester de proline-rapamycine 42 avec acide propionique de 2,2-bis(hydroxyméthyle) (proline-CCI-779) et un procédé de préparation régiospécifique d'ester de rapamycine 42 ou de proline-rapamycine 42 avec acide propionique de 2,2-bis(hydroxyméthyle) (CCI-779 et proline-CCI-779) : (a) réaction entre rapamycine ou proline-rapamycine et dérivé d'ester activé d'acide propionique de 2,2-bis(hydroxyméthyle) de structure (I) sachant que R¿1? et R¿2? sont hydrogène, ou pris ensemble pour former un cétal de structure (II) sachant que R¿3? and R¿4? sont chacun, indépendamment, hydrogène, alkyle C¿1-6?, linéaire ou ramifié, ou pris ensemble pour former cycloalkyle C¿5-7? ou pris ensemble pour former un boronate cyclique de structure (III), sachant que R¿5? peut être méthyle, éthyle, n-propyle, iso-propyle, n-butyle, iso-butyle et phényle; la réaction est conduite dans un solvant organique approprié en présence d'une quantité efficace de lipase microbienne; et (b) déprotection de l'intermédiaire issu de l'étape (a), pour donner le produit CCI-779 ou proline-CCI-779.

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