Dinucleotide analogues, intermediates therefor and oligonucleotides derived therefrom

摘要

A compound of formula where R<1> is hydrogen, R<1>a or a group of formula R<1>a is R<1>b or a protecting group Q, R<1>b is C1-C20 alkyl, C2-C20 alkenyl, C3-C10 cycloalkyl, C6-C15 aryl, C7-C16 aralkyl or a 5- or 6- membered heterocyclic group attached by a carbon atom in the heterocyclic group to the indicated phosphorus atom, R<2> is an unsubstituted or substituted C1-C20 alkyl or C2-C20 alkenyl group, an unsubstituted or substituted C3-C10 cycloalkyl group, an unsubstituted or substituted C6-C15 aryl group, an unsubstituted or substituted C7-C16 aralkyl group, or a 5- or 6- membered heterocyclic group attached by a carbon atom in the heterocyclic group to the indicated phosphorus atom, R<3> is hydrogen, halogen, hydroxy, R<1><5>, -OR<1><5> or -OSO2R<1><5> R<4> is R<4>a or together with R<6> denotes a valence bond, R<4>a is hydrogen, halogen or R<1><6>, R<5> is hydrogen, halogen, hydroxy, R<1><7>, -OR<1><7>, -OCOR<1><7> or -OSO2R<1><7>, R<6> is hydrogen, halogen or R<1><8>, or together with R<4> denotes a valence bond, R<7> is hydrogen, alkyl-N, N-dialkylphosphoramidyl or R<7>a, or R<7>O- together with R<8>a denotes a C1-C15 hydrocarbylidenedioxy group, R<7>a is R<1><9>, -COR<1><9>, -SO2R<1><9> or tri(C1-C15 hydrocarbyl)silyl, R<8> is R<8>a or Z, R<8>a is hydrogen, halogen, hydroxy, R<2><0>, -OR<2><0>, -OCOR<2><0>, -OSO2R<2><0>, or tri(C1-C15 hydrocarbyl)silyloxy, or together with R<9> denotes a C1-C15 hydrocarbylidenedioxy group, or together with R<7>O- denotes a C1-C15 hydrocarbylidenedioxy group, R<9> is halogen, hydroxy, -OR<2><1>, -OCOR<2><1>, -OSO2R<2><1>, or B<2>, or together with R<8>a denotes a C1-C15 hydrocarbylidenedioxy group, R<1><0> is hydrogen or R<1><0>a, R<1><0>a is R<2><2>, -COR<2><2>, -SO2R<2><2> or tri(C1-C15 hydrocarbyl)silyl, R<1><1> is hydrogen, halogen, hydroxy, R<2><3>, -OR<2><3>, -OCOR<2><3>, -OSO2R<2><3> or Z, R<1><2> is hydrogen, halogen or R<2><4>, R<1><3> is R<1><3>a or Z, R<1><3>a is hydrogen, halogen, hydroxy, R<2><5>, -OR<2><5>, -OCOR<2><5>, -OSO2R<2><5>, or tri(C1-C15 hydrocarbyl)silyloxy, or together with R<1><4> denotes a C1-C15 hydrocarbylidenedioxy group, R<1><4> is halogen, hydroxy, -OR<2><6>, -OCOR<2><6>, -OSO2R<2><6>, or B<1>, or together with R<1><3>a denotes a C1-C15 hydrocarbylidenedioxy group, R<1><5>, R<1><6>, R<1><7>, R<1><8>, R<1><9>, R<2><0>, R<2><1>, R<2><2>, R<2><3>, R<2><4>, R<2><5> and R<2><6> are independently a C1 to C10 aliphatic group, a C3 to C10 cycloaliphatic group, a C6 to C15 aromatic group or a C7-C30 araliphatic group, B<1> and B<2> are independently each a monovalent nucleoside base radical, and Z is substituted or unsubstituted C6-C10 aryloxythiocarbonyloxy; provided that compounds where simultaneously R<1>, R<3>, R<4> and R<6> are hydrogen, R<2> is isopropyl, R<5> is methoxy, R<7> is methyl, R<8> and R<9> are each hydroxy or each acetoxy or R<8> and R<9> together denote isopropylidenedioxy, compounds where simultaneously R<1>, R<3>, R<4> and R<6> are hydrogen, R<2> is butyl, R<5> is methoxy, R<7> is benzyl, R<8> and R<9> are each hydroxy or each acetoxy or R<8> and R<9> together denote isopropylidenedioxy, and compounds where simultaneously R<1>, R<3>, R<4>, R<5>, R<6> and R<7> are hydrogen, R<2> is phenyl and R<8> and R<9> together denote isopropylidenedioxy are excluded.