First regioselective enzymatic alkoxycarbonylation of primary amines. Synthesis of novel 5'- and 3'-carbamates of pyrimidine 3',5'-diaminonucleoside derivatives including BVDU analogues.
The first regioselective enzymatic alkoxycarbonylation of primary amino groups has been achieved in pyrimidine 3',5'-diaminonucleoside derivatives. Thus, Candida antarctica lipase B (CAL-B) catalyzed this reaction with nonactivated homocarbonates allowing the selective synthesis of several N-5' carbamates, including (E)-5-(2-bromovinyl)-2'-deoxyuridine (BVDU) analogues, with moderate-high yields, whereas immobilized Pseudomonas cepacia lipase (PSL-C) afforded mixtures of alkoxycarbonylated regioisomers. To obtain N-3' carbamates selectively, a short and efficient chemoenzymatic route was used employing some of the N-5'-protected derivatives previously synthesized.
Departamento de Química Orgánica e Inorgánica, Facultad de Química, Universidad de Oviedo, 33071-Oviedo, Spain.
Iván
I
Lavandera
Susana
S
Fernández
Miguel
M
Ferrero
Vicente
V
Gotor
D000588:Amines / Q000737:chemistry*; D001973:Bromodeoxyuridine / Q000031:analogs & derivatives* / Q000138:chemical synthesis* / Q000737:chemistry; D002219:Carbamates / Q000138:chemical synthesis* / Q000737:chemistry; D004800:Enzymes, Immobilized / Q000378:metabolism; D005656:Fungal Proteins; D008049:Lipase / Q000378:metabolism; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009705:Nucleosides / Q000138:chemical synthesis* / Q000737:chemistry; D011743:Pyrimidines / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D000588:Amines; D002219:Carbamates; D004800:Enzymes, Immobilized; D005656:Fungal Proteins; D009705:Nucleosides; D011743:Pyrimidines; D008049:Lipase; C431349:lipase B, Candida antarctica; D001973:Bromodeoxyuridine