Methods of producing phosphitylated compounds

C - Chemistry – Metallurgy – 07 – B

Patent

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C07B 47/00 (2006.01) C07F 9/24 (2006.01) C07H 19/10 (2006.01) C07H 19/20 (2006.01) C07H 21/00 (2006.01)

Patent

CA 2477039

Provided are methods of producing phosphitylated compounds, including 3'- O~phosphoramidites, comprising the step of reacting a hydroxyl-containing compound with a phosphitylating agent in the presence of a phosphitylation activator selected from the group consisting of (1) acid-base complexes derived from an amine base of Formula (I) wherein R, R1, and R2 are independently C1-C10 alkyl, C1-C10 cycloalkyl, C1-Cl0 aryl, Cl-C10 aralkyl, Cl- C10 heteroalkyl, or Cl-CIO heteroaryl; (2) acid-base complexes derived from an amine base of Formula (II) wherein R3, R4, R5, R6, and are independently hydrogen, C1-C10 alkyl, Cl-C10 cycloalkyl, Cl-C10 aryl, Cl-CIO aralkyl, Cl-CIO heteroalkyl, or C1-C10 heteroaryl, and at least one of R3, R4, R5, R6, and R7 is not hydrogen.; (3) acid-base complexes derived from a diazabicyclo amine base; (4) zwitterionic amine complexes; and (5) combinations of two or more thereof, to produce a phosphitylated compound.

L'invention porte sur des procédés de production de composés phosphitylés dont des 3'-O-phosphoramidites, comprenant les étapes suivantes: réaction d'un composé à radicaux hydroxyle avec un agent phosphitylateur en présence d'un activateur de phosphitylation choisi parmi (1) des complexes acide-base dérivant d'une base aminée de formule (I) dans laquelle: R, R?1¿, et R?2¿ sont indépendamment C¿1?-C¿10? alkyle, C¿1?-C¿10? cycloalkyle, C¿1?-C¿l0? aryle, C¿l?-C¿10? aralkyle, C¿l?-C¿10? hétéroalkyle, ou C¿l?-C<SB>IO</SB> hétéroaryle; (2) des complexes acide-base dérivant d'une base aminée de formule (II) dans laquelle: R?3¿, R?4¿, R?5¿, R?6¿, et R?7 ¿sont indépendamment hydrogène, C¿1?-C¿10? alkyle, C¿l?-C¿10? cycloalkyle, C¿l?-C¿10? aryle, C¿l?-C<SB>IO</SB> aralkyle, C¿l?-C<SB>IO</SB> hétéroalkyle, ou C¿1?-C¿10? hétéroaryle, et au moins l'un des R?3¿, R?4¿, R?5¿, R?6¿, et R?7¿ n'est pas hydrogène; (3) des complexes acide-base dérivant d'une base diazabicyclo amine; (4) des complexes zwitterioniques amino; et (5) des combinaisons de deux ou plusieurs d'entre eux, de façon à obtenir le composé phosphitylé.

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