Use of 13C as an indirect tag in 15N specifically labeled nucleosides. Syntheses of [8-13C-1,7,NH2-15N3]adenosine, -guanosine, and their deoxy analogues.
We have previously reported the use of a 13C tag at the C2 of 15N-multilabeled purine nucleosides to distinguish the adjacent-labeled 15N atoms from those in an untagged nucleoside. We now introduce the use of an indirect tag at the C8 of 15N7-labeled purine nucleosides. This tag allows unambiguous differentiation between a pair of 15N7-labeled purines in which only one is 13C8 labeled. Although the very small C8-N7 coupling (<1 Hz) precludes its direct detection in 1D 15N spectra, 2D 1H-15N NMR experiments display the large C8-H8 coupling (>200 Hz) because H8 is coupled to both N7 and C8. The 13C8 atom is introduced by means of a ring closure of the exocyclic amino groups of a pyrimidinone using [13C]sodium ethyl xanthate. Here, we present methods for the syntheses of [8-13C-1,7,NH2-15N3]adenosine, -guanosine, and their deoxy analogues.
Shallop
Anthony J
AJ
Department of Chemistry and Chemical Biology, Rutgers, The State University of New Jersey, Piscataway, New Jersey 08854, USA.
Gaffney
Barbara L
BL
Jones
Roger A
RA
D000241:Adenosine / Q000138:chemical synthesis*; D002247:Carbon Isotopes; D003839:Deoxyadenosines / Q000138:chemical synthesis; D003849:Deoxyguanosine / Q000138:chemical synthesis; D006151:Guanosine / Q000138:chemical synthesis*; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D009587:Nitrogen Isotopes; D009705:Nucleosides / Q000138:chemical synthesis*; D011741:Pyrimidine Nucleosides / Q000737:chemistry; D013871:Thiones / Q000737:chemistry
D002247:Carbon Isotopes; D003839:Deoxyadenosines; D009587:Nitrogen Isotopes; D009705:Nucleosides; D011741:Pyrimidine Nucleosides; D013871:Thiones; D006151:Guanosine; C004918:ethylxanthate; D003849:Deoxyguanosine; D000241:Adenosine