5-modified pyrimidines from palladium catalyzed carbon-carbon coupling

• US 5,591,843 A
• Filed: 04/19/1995
• Issued: 01/07/1997
• Est. Priority Date: 06/14/1993
• Status: Expired due to Term

• Current Assignee: Bruce Eaton
• Original Assignee: Bruce Eaton
• Inventors: Eaton, Bruce
• Primary Examiner(s): Wilson, James O.
• Application Number:
  US08/423,395
• Time in Patent Office: 629 Days
• Field of Search: 536/28.1, 536/28.4, 536/28.5, 536/28.51, 536/28.52, 536/28.53, 536/28.54
• US Class Current: 536/28.52
• CPC Class Codes: B01J 2231/4255 Stille-type, i.e. RY + R'3SnR'', in which R is alkenyl, aryl, R' is alkyl and R'' is alkenyl or aryl
• CPC Class Codes: B01J 2531/824 Palladium
• CPC Class Codes: B01J 31/2404 Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
• CPC Class Codes: C07H 19/06 Pyrimidine radicals
• CPC Class Codes: C07H 19/10 with the saccharide radical esterified by phosphoric or polyphosphoric acids
• CPC Class Codes: C07H 19/16 Purine radicals
• CPC Class Codes: C07H 19/20 with the saccharide radical esterified by phosphoric or polyphosphoric acids
• CPC Class Codes: C07H 21/00 Compounds containing two or more mononucleotide units having separate phosphate or polyphosphate groups linked by saccharide radicals of nucleoside groups, e.g. nucleic acids

Abstract

This invention discloses a method for the preparation of pyrimidine nucleosides modified at the 5-position of the pyrimidine ring using a palladium catalyst of the formula PdL₃, wherein L is a ligand of palladium. Included in the invention are pyrimidine nucleosides modified at the 5-position prepared according to the method of the invention.

Claims

1. A pyrimidine nucleoside modified at the 5-position of the pyrimidine ring prepared according to a method comprising the steps of:

a) preparing a solution of a palladium catalyst of the formula PdL₃, wherein L is triphenylphosphine (PPh₃);

b) reacting a pyrimidine starting material containing a halogen leaving group attached to the 5-position of said pyrimidine starting material with a tetraalkyl tin compound of the formula R'"'"'SnR"₃, wherein R'"'"' is a C1 to C4 alkyl, and R" is selected from the group consisting of a C1 to C7 carbonyl, a C1 to C5 carbalkoxy, a C1 to C3 alkenyl, a C1 to C4 alkoxy or phenyl (C₆ H₅), in the presence of the PdL₃ catalyst; and

c) isolating and purifying said pyrimidine nucleoside.

2. A compound of the formula ##STR13## wherein R₁, R₂ and R₃ are independently H, alkyl, alkenyl, alkynyl, alkoxy, phenyl or halo and Y is ribose or deoxyribose.

3. A compound of the formula:

##STR14## wherein R₁, R₂, R₃, R₄ and R⁵ are independently halo, H, alkyl, alkynyl, alkoxyl, phenyl or cyano and Y is ribose or deoxyribose.